Communications
CED MATERIALS
mono-thiophene (N-[(6-(thien-3-yl)hexanoyloxy]-pyrroli-dine-2,5-dione; see Scheme 1) instead of the bithiophene derivative, we have been able to prepare analogous glucose oxidase-modified polymer films. The functionalized polythiophene film has been obtained using a similar multisweep regime, however, with potential scans up to a vertex potential of 1.7 V vs. SCE, reflecting the higher potential of the radical cations formation. The second step, the covalent immobilization of the enzyme is of course equivalent and independent from the specific needs for the formation of the polymer film. The obtained enzyme electrodes show a slightly lower response as those obtained with the functionalized poly(bithiophene) films, despite there are double active ester groups available to react with the enzyme. Probably, due to the size of an individual enzyme molecule the increased number of binding sites at the electrode surface does not concomitantly increase the immobilized enzyme activity.To conclude, we have shown that, despite the high oxidation potential of thiophene and its derivatives, polythiophene films can be advantageously used for the entrapment or covalent immobilization of enzymes. This was realized by entrapment of glucose oxidase using dimeric or trimeric thiophenes as parent compounds for the polymerization process in CH3CN/water mixtures or, according to a two-step procedure, based on functionalized polythiophene or poly(bithi0phene) films and covalently bound enzyme. In principle, polythiophene as immobilization matrix in amperometric enzyme electrodes has at least two advantages over other conducting polymer films: First, derivatization of thiophene in the 3-position and the synthesis of oligomers is much easier than for pyrrole. Second, due to the higher redox potential of the polymer film itself, deterioration e.g. by enzymatically generated H202 is less probable. This is even more important for a next sensor generation, in which the conducting polymer is expected to act as molecular wire between the active site of the enzyme and the electrode surface. Possibly, the improved stability of polythiophene against oxidation in ambient environments will allow the construction of biosensors with improved sensor characteristics and life-time.Some organisms form stable minerals that would never precipitate under ambient conditions in an inorganic environment, or, if formed, are unstable precursors of more stable compounds.['321 One of the most fascinating examples is biogenic amorphous calcium carbonate, because its transformation into crystalline polymorphs is not only thermodynamically favored, but also kinetically fast.I3] We report here an example of a single skeletal element, spicules from the calcareous sponge Clathrina, composed of crystalline calcite in one layer and stable amorphous CaC03 in another. Differential dissolution of the amorphous phase of these spicules released macromolecules with proteins rich in glutamic acid (and/or glutamine), serine, glycine and polysaccharide...