Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt-based Electrocatalysts – Part II: Effect of Platinum Dispersion

We investigated the oxygen reduction reaction (ORR) mechanism on Pt nanoparticles (NPs) dispersed on several carbon blacks with various physicochemical properties (i. e. specific surface ranging from 80 to 900 m² g⁻¹, different graphitization degree, etc.). Using the kinetic isotope effect (KIE) along with various electrochemical characterizations, we determined that the rate determining step (RDS) of the ORR is a proton-independent step when the density of Pt NPs on the surface of the carbon support is high. Upon decrease of the density of Pt NPs on the surface, the RDS of the ORR starts involving a proton, as denoted by an increase of the KIE >1. This underlined the critical role played by the carbon support in the oxygen reduction reaction electrocatalysis by Pt supported on high surface area carbon.     

CTI: A novel charge-related topological index with low degeneracy

A new type of topological index is proposed. Its definition is based on the concept of atomic charge distributions in organic molecules. Introduction of electronic in addition to purely topologic factors allows consideration of heteroatom-containing structures as well. It is demonstrated that the index has a low degree of degeneracy, thus suggesting it can be used for coding chemical structures, discrimination of redundancies in structure generation programs, and studies of quantitative structure-activity relationships for heteroatom-containing structures.     

Engineering of glucose oxidase for direct electron transfer via site-specific gold nanoparticle conjugation

Optimizing the electrical communication between enzymes and electrodes is critical in the development of biosensors, enzymatic biofuel cells, and other bioelectrocatalytic applications. One approach to address this limitation is the attachment of redox mediators or relays to the enzymes. Here we report a simple genetic modification of a glucose oxidase enzyme to display a free thiol group near its active site. This facilitates the site-specific attachment of a maleimide-modified gold nanoparticle to the enzyme, which enables direct electrical communication between the conjugated enzyme and an electrode. Glucose oxidase is of particular interest in biofuel cell and biosensor applications, and the approach of "prewiring" enzyme conjugates in a site-specific manner will be valuable in the continued development of these systems.     

Enantioselective Titanium(III)-Catalyzed Reductive Cyclization of Ketonitriles

Reduction, please! The title reaction affords α-hydroxyketones, a common structural motif in biologically active natural products, in good yields and high enantioselectivities at room temperature. The commercially available ansa-titanocene 1 was found to be an efficient catalyst for this process, which presumably proceeds by addition of a ketyl radical to a nitrile.     

Nonlinear equations for the recurrence coefficients of discrete orthogonal polynomials

We study polynomials orthogonal on a uniform grid. We show that each weight function gives two potentials and each potential leads to a structure relation (lowering operator). These results are applied to derive second order difference equations satisfied by the orthogonal polynomials and nonlinear difference equations satisfied by the recursion coefficients in the three-term recurrence relations.     

Modified construction of nuclear Fréchet spaces without basis

Recently, B. Mitiagin and N. Zobin constructed an example of nuclear Fréchet space without basis. The essential modification of their constructions gives the following results. There exists such a nuclear Fréchet space X that for any nuclear Fréchet space Y the space X × Y has no basis (Sections 1 and 2). This fact has a lot of corollaries (Sect. 3); e.g., the space X × C^∞(R¹) having the maximal diametral dimension among nuclear Fréchet spaces nevertheless has no basis. One can also construct (Sect. 4) a nuclear Fréchet space $\text{X}\text{?}$ without strongly finite-dimensional decomposition (see Definition 0.1). In Section 5 some comments and open questions are given.     

Phototransistor noise model based on noise measurements on PNP PIN phototransistors

A noise model for phototransistors in open base configuration is presented. The model was developed from the noise measurements on four different phototransistor designs. The extracted current gains from the noise model were verified by measured current gains from Gummel measurements. Furthermore the current noise spectral density was modeled and compared with the noise measurements. A difference of less than 12 % in the current gain was achieved. In addition to the extracted current gains also the most dominant shot noise terms including their values of each phototransistor are extracted.     

From 1/f noise to multifractal cascades in heartbeat dynamics

We explore the degree to which concepts developed in statistical physics can be usefully applied to physiological signals. We illustrate the problems related to physiologic signal analysis with representative examples of human heartbeat dynamics under healthy and pathologic conditions. We first review recent progress based on two analysis methods, power spectrum and detrended fluctuation analysis, used to quantify long-range power-law correlations in noisy heartbeat fluctuations. The finding of power-law correlations indicates presence of scale-invariant, fractal structures in the human heartbeat. These fractal structures are represented by self-affine cascades of beat-to-beat fluctuations revealed by wavelet decomposition at different time scales. We then describe very recent work that quantifies multifractal features in these cascades, and the discovery that the multifractal structure of healthy dynamics is lost with congestive heart failure. The analytic tools we discuss may be used on a wide range of physiologic signals. (c) 2001 American Institute of Physics.