Enhanced Power Density of Alcohol Biofuel Cell by Polymer-assisted Crosslinks of 3D Graphene on Carbon Paper as the Bioanode

Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device.     

Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms

The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐Co^II derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear Co^II center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered.     

pH-Sensitive Oscillatory Motion of a Urease Motor on the Urea Aqueous Phase

A self-propelled object coupled with an enzyme reaction between urease and urea was investigated at the air/aqueous interface. A plastic object that was fixed to a urease-immobilized filter paper was used as a self-propelled object, termed a urease motor, placed on an aqueous urea solution. The driving force of the urease motor is the difference in the surface tension around the object. Oscillatory motion or no motion was triggered depending on the initial pH of the urea solution. Both the frequency and maximum speed of the oscillatory motion varied depending on the initial pH of the water phase. The mechanisms underlying the oscillatory motion and no motion were discussed in relation to the bell-shaped enzyme activity of urease in the enzyme reaction and the surface tension around the urease motor.     

Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases

Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts.     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine （Co2Pc2） and binuclear ferric phthalocyanine （Fe2Pc2）, were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives （Mt2Pc2） were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.     

A Large Conformational Change of a Bridged b-Cyclodextrin Dimer in Aqueous Solution

As artificial enzymes, the binding constants of cyclodextrins (CDs) and their substrates are expected to be high1. For this purpose, many kinds of bridged cyclodextrin dimers2 whose two cyclodextrins are linked by various spacers have been constructed. It was of interest to make the dimers, whose binding constants would exceed 108dm3/mol3. Up to date, the bridged cyclodextrin dimers have been extensively studied as enzyme models and as molecular receptors4-6. Recently, we synthesized a brid…     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Über die Magnetischen Eigenschaften der Cobaltate Na6CoS4, Na6CoSe4 und K6CoS4

Magnetic Properties of the Cobaltates Na₆CoS₄, Na₆CoSe₄, and K₆CoS₄ The alkali metal cobalt chalcogenides Na₆CoS₄, Na₆CoSe₄, and K₆CoS₄ crystallize in the space group P6₃mc with Z = 4. The structure is characterized by isolated [CoX₄]-tetrahedra. The magnetic susceptibilities show Curie-Weiss behaviour. The deviations at low temperatures are caused by antiferromagnetic interactions. The magnetic moments are discussed with regard to ligand-field parameters.     

Flow-injection determination of 3-hdroxybutyrate in serum with an immobilized 3-hydroxybutyrate dehydrogenase reactor and chemiluminescence detection

A flow-injection system for the determination of 3-hydroxybutyrate in serum is described. 3-Hydroxybutyrate dehydrogenase is immobilized on poly(vinyl alcohol) beads and incorporated in a flow-injection system. 1-Methoxy-5-methylphenazinium methylsulphate reacts with enzymatically generated NADH to give H₂O₂, which is detected chemiluminometrically with the reaction of luminol and hexacynoferrate(III). Serum is diluted and filtered through an ultrafiltration membrane. The system responds linearly to injected samples (80 μl) in the concentration range 0.5–300 μM; the detection limit is 0.1 μM. The within-day relative standard deviation (n = 90) for 58 μM 3-hydroxybutyrate in serum is 0.8%. The maximum throughout is 20 samples per hour. The immobilized enzyme is stable for at least 1 month.