Fibre optic fluorometric enzyme sensors for hydrogen peroxide and lactate,based on horseradish peroxidase and lactate oxidase

An optical biosensor for the determination of hydrogen peroxide based on immobilized horseradish peroxidase is described. The fluorescence of the dimeric product of the enzyme catalysed oxidation of homovanillic acid is utilized to determine the concentration of H₂O₂. The membrane-bound enzyme is attached to a bifurcated fibre bundle permitting excitation and detection of the fluorescence by a fluorometer. The response of the sensor is linear from 1 to 130 M hydrogen peroxide; the coefficient of variation is 3%. The sensor is stable for more than 10 weeks. The operating pH for maximal sensor response is 8.15. This allows the sensor to be used in combination with oxidase reactions producing hydrogen peroxide, as is demonstrated with a co-immobilized lactate oxidase-horseradish peroxidase optode for the determination of L-lactate. The fluorescence intensity of this sensor depends linearly on the concentration of lactate between 3 and 200 M and a throughput of 10 samples per hour is possible. The precision is in the same range as that of the monoenzyme optode. The lifetime of the bienzyme sensor for lactate is considerably shorter than that of the peroxidase sensor; it is limited by the stability of the immobilized lactate oxidase enzyme. The sensor has been applied to the determination of lactate in control serum.     

Crystal structure of ethene-/α-olefin copolymers with various long comonomers (C8–C26)

Ethene-/α-olefin copolymers having a wide range of comonomers between 8 and 26 carbon atoms in length were characterized by wide angle X-ray diffraction (WAXD). It was found that the crystallinities for the shorter comonomers (C₈, C₁₂) matched fairly well with the crystallinities from DSC and volumetric measurements, while for the longer comonomers (C₁₈, C₂₆) distinct differences between the three methods were found. This was explained by the presence of an additional crystalline phase of the side chains slightly deforming the amorphous peak.     

Unravelling the mechanism of glycerol hydrogenolysis over rhodium catalyst through combined experimental-theoretical investigations

We report herein a detailed and accurate study of the mechanism of rhodium-catalysed conversion of glycerol into 1,2-propanediol and lactic acid. The first step of the reaction is particularly debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary reactions can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally. On the other hand, there was a lack of knowledge about the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of density functional theory (DFT) to describe the above-mentioned elementary reactions and to calculate the corresponding transition states. The combination of experiment and theory shows that the dehydrogenation into glyceraldehyde is the first step for the glycerol transformation on the Rh/C catalyst in basic media under He or H(2) atmosphere.     

Temperature change from isenthalpic expansion of aqueous triethylene glycol mixtures for natural gas dehydration

In natural gas dehydration units, rich TEG solutions are decompressed before the TEG regeneration stage and the direction of the temperature change during the decompression has been debated. The temperature change from an isenthalpic expansion from (7000 kPa to 440 kPa was measured for the following aqueous mixtures: pure water, 99% pure triethylene glycol (TEG), aqueous TEG (99 wt% TEG + 1% water), aqueous TEG saturated with methane, aqueous TEG saturated with n-pentane, and aqueous TEG saturated with n-heptane. In all cases, the temperature increased upon expansion with the magnitude of the temperature change ranging from 1.4 K for pure water to 2.4 K for TEG. A simple equation of state model predicted the correct direction for the temperature change and the predicted values were within ±1 K of the experimental data.     

Hidden Brønsted acid catalysis: pathways of accidental or deliberate generation of triflic acid from metal triflates

The generation of a hidden Br?nsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF(3)SO(3)H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl(2)/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Br?nsted acid catalyst useful for mechanistic control experiments or for synthetic applications.     

Chemical mimicry: hierarchical 1D TiO2@ZrO2 core-shell structures reminiscent of sponge spicules by the synergistic effect of silicatein-α and silintaphin-1

In nature, mineralization of hard tissues occurs due to the synergistic effect of components present in the organic matrix of these tissues, with templating and catalytic effects. In Suberites domuncula, a well-studied example of the class of demosponges, silica formation is mediated and templated by an axial proteinaceous filament with silicatein-α, one of the main components. But so far, the effect of other organic constituents from the proteinaceous filament on the catalytic effect of silicatein-α has not been studied in detail. Here we describe the synthesis of core-shell TiO(2)@SiO(2) and TiO(2)@ZrO(2) nanofibers via grafting of silicatein-α onto a TiO(2) nanowire backbone followed by a coassembly of silintaphin-1 through its specifically interacting domains. We show for the first time a linker-free, one-step funtionalization of metal oxides with silicatein-α using glutamate tag. In the presence of silintaphin-1 silicatein-α facilitates the formation of a dense layer of SiO(2) or ZrO(2) on the TiO(2)@protein backbone template. The immobilization of silicatein-α onto TiO(2) probes was characterized by atomic force microscopy (AFM), optical light microscopy, and high-resolution transmission electron microscopy (HRTEM). The coassembly of silicatein-α and silintaphin-1 may contribute to biomimetic approaches that pursue a controlled formation of patterned biosilica-based biomaterials.