Enhancement of the performances of a single concentric glucose/O2 biofuel cell by combination of bilirubin oxidase/Nafion cathode and Au–Pt anode

This work deals with a novel preparation method of bilirubin oxidase/2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid electrode. The enzyme and its mediator were adsorbed on carbon Vulcan XC-72R before their immobilization into a Nafion^® matrix. Promising results were obtained when this biocathode was associated with Au₇₀Pt₃₀ nanoparticles as anode in a single concentric glucose/O₂ biofuel cell (BFC). The latter BFC delivered at 37 °C a power density of 90 μW cm^?2 for a cell voltage of 0.4 V in phosphate buffer (pH 7.4) containing 0.01 M glucose. Moreover, the electrical performances were increased with the concentration of glucose by generating up to 190 μW cm^?2 for a cell voltage of 0.52 V when the concentration of the renewable fuel reached 0.7 M.     

History of individuals of the 18th/19th centuries stored in bones,teeth, and hair analyzed by LA–ICP–MS—a step in attempts to confirm the authenticity of Mozart’s skull

A cranium stored in the Stiftung Mozarteum in Salzburg/Austria which is believed to be that of Mozart, and skeletal remains of suspected relatives which have been excavated from the Mozart family grave in the cemetery in Salzburg, have been subjected to scientific investigations to determine whether or not the skull is authentic. A film project by the Austrian television ORF in collaboration with Interspot Film on this issue was broadcast at the beginning of the “Mozart year 2006”. DNA analysis could not clarify relationships among the remains and, therefore, assignment of the samples was not really possible. In our work this skull and excavated skeletal remains have been quantified for Pb, Cr, Hg, As, and Sb content by laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS) to obtain information about the living conditions of these individuals. A small splinter of enamel (less than 1 mm³) from a tooth of the “Mozart cranium” was also available for investigation. Quantification was performed by using spiked hydroxyapatite standards. Single hair samples which are recorded to originate from Mozart have also been investigated by LA–ICP–MS and compared with hair samples of contemporary citizens stored in the Federal Pathologic–Anatomical Museum, Vienna. In general, Pb concentrations up to approximately 16 μg g⁻¹ were found in the bone samples of 18th century individuals (a factor of 7 to 8 higher than in recent samples) reflecting elevated Pb levels in food or beverages. Elevated Pb levels were also found in hair samples. The amount of Sb in the enamel sample of the “Mozart cranium” (approx. 3 μg g⁻¹) was significantly higher than in all the other tooth samples investigated, indicating possible Sb ingestion in early childhood. Elevated concentrations of elements in single hair samples gave additional information about possible exposure of the individuals to heavy metals at a particular point in their life.     

Room temperature preparation of α-chloro-β,β-difluoroethenylzinc reagent (CF2CClZnCl) by the metallation of HCFC-133a (CF3CH2Cl) and a high yield one-pot synthesis of α-chloro-β,β-difluorostyrenes

α-Chloro-β,β-difluorovinylzinc reagent [CF₂CClZnCl] was generated in 91% yield by the metallation of a THF solution of commercially available HCFC-133a (CF₃CH₂Cl) and zinc chloride at 15-20 °C using LDA as base. The corresponding reaction with Halothane™ (CF₃CHClBr) produced a poor yield of CF₂CClZnCl. The palladium catalyzed coupling reaction of the CF₂CClZnCl with aryl iodides under mild reaction conditions produced α-chloro-β,β-difluorostyrenes in 64-90% isolated yields. The stability of the intermediate CF₂CClLi and the nature of the zinc reagents are discussed.     

Hexadecahydrotetrabenzo[a,c,d,f]fluorene - Ligand, available by Friedel-Crafts fluorene cycloalkylation. Synthesis, crystal and molecular structure of (η-C29H34)(η-C5H5)ZrCl2

Friedel-Crafts cycloalkylation of fluorene with 1,4-dichlorobutane has been studied in different conditions. This reaction allows to obtain the product of exhausting fluorene alkylation, hexadecahydrotetrabenzo[a,c,d,f]fluorene - perspective η⁵ ligand. The simplest zirconocene has been synthesized and its structure has been confirmed by X-ray diffraction analysis. The molecule of this compound possesses skewed conformation of metallocene fragment with the phenylene moiety of fluorenyl ligand oriented towards the front side of metallocene wedge.     

Well-defined critical association concentration and rapid adsorption at the air/water interface of a short amphiphilic polymer, amphipol A8-35: a study by Förster resonance energy transfer and dynamic surface tension measurements

Amphipols (APols) are short amphiphilic polymers designed to handle membrane proteins (MPs) in aqueous solutions as an alternative to small surfactants (detergents). APols adsorb onto the transmembrane, hydrophobic surface of MPs, forming small, water-soluble complexes, in which the protein is biochemically stabilized. At variance with MP/detergent complexes, MP/APol ones remain stable even at extreme dilutions. Pure APol solutions self-associate into well-defined micelle-like globules comprising a few APol molecules, a rather unusual behavior for amphiphilic polymers, which typically form ill-defined assemblies. The best characterized APol to date, A8-35, is a random copolymer of acrylic acid, isopropylacrylamide, and octylacrylamide. In the present work, the concentration threshold for self-association of A8-35 in salty buffer (NaCl 100 mM, Tris/HCl 20 mM, pH 8.0) has been studied by F?rster resonance energy transfer (FRET) measurements and tensiometry. In a 1:1 mol/mol mixture of APols grafted with either rhodamine or 7-nitro-1,2,3-benzoxadiazole, the FRET signal as a function of A8-35 concentration is essentially zero below a threshold concentration of 0.002 g·L(-1) and increases linearly with concentration above this threshold. This indicates that assembly takes place in a narrow concentration interval around 0.002 g·L(-1). Surface tension measurements decreases regularly with concentration until a threshold of ca. 0.004 g·L(-1), beyond which it reaches a plateau at ca. 30 mN·m(-1). Within experimental uncertainties, the two techniques thus yield a comparable estimate of the critical self-assembly concentration. The kinetics of variation of the surface tension was analyzed by dynamic surface tension measurements in the time window 10 ms-100 s. The rate of surface tension decrease was similar in solutions of A8-35 and of the anionic surfactant sodium dodecylsulfate when both compounds were at a similar molar concentration of n-alkyl moieties. Overall, the solution properties of APol "micelles" (in salty buffer) appear surprisingly similar to those of the micelles formed by small, nonpolymeric surfactants, a feature that was not anticipated owing to the polymeric and polydisperse nature of A8-35. The key to the remarkable stability to dilution of A8-35 globules, likely to include also that of MP/APol complexes, lies accordingly in the low value of the critical self-association concentration as compared to that of small amphiphilic analogues.     

Synthesis,structure and properties of cobalt(II/III) seleno-bisphenolate complexes containing NN bidentate co-ligands: kinetic studies on the reduction of a cobalt(III) complex by ascorbic acid in 80% MeCN–20% water

Two cobalt complexes, [Co(L^Se)(phen)] · CH₂Cl₂ (1) and [Co(L^Se)(N,N-Me₂en)(CH₃COO⁻)] (2) have been synthesized and characterized by elemental analyses, magnetic measurements, i.r. studies etc. Single crystal X- ray studies reveal that in complex (1) cobalt atom is in +2 oxidation state with trigonal bipyramidal geometry, while in complex (2) it is in +3 oxidation state and surrounded octahedrally. The asymmetric unit of complex (2) contains two crystallographically independent discrete molecules. Complex (1) was found to be paramagnetic with μ_eff = 2.19 BM indicating a low spin cobalt(II) d⁷ system, whereas complex (2) is found to be diamagnetic with cobalt(III) in low spin d⁶ state. The kinetic studies on the reduction of (2) by ascorbic acid in 80% MeCN–20% H₂O (v/v) at 25 °C reveal that the reaction proceeds through the rapid formation of inner-sphere adduct, probably by replacing the loosely coordinated AcO⁻ group, followed by electron transfer in a slow step and is supported by a large Q (formation constant) value.