Analysis of Hydrogen Tunneling in an Enzyme Active Site using von Neumann Measurements

We build on our earlier quantum wavepacket study of hydrogen transfer in the biological enzyme, soybean lipoxygenase-1, by using von Neumann quantum measurement theory to gain qualitative insights into the transfer event. We treat the enzyme active site as a measurement device which acts on the tunneling hydrogen nucleus via the potential it exerts at each configuration. A series of changing active site geometries during the tunneling process effects a sequential projection of the initial, reactant state onto the final, product state. We study this process using several different kinds of von Neumann measurements and show how a discrete sequence of such measurements not only progressively increases the projection of the hydrogen nuclear wavepacket onto the product side but also favors proton over deuteron transfer. Several qualitative features of the hydrogen tunneling problem found in wavepacket dynamics studies are also recovered here. These include the shift in the "transition state" towards the reactant as a result of nuclear quantization, greater participation of excited states in the case of deuterium, and presence of critical points along the reaction coordinate that facilitate hydrogen and deuterium transfer and coincide with surface crossings. To further "tailor" the dynamics, we construct a perturbation to the sequence of measurements, that is a perturbation to the dynamical sequence of active site geometry evolution, which leads us to insight on the existence of sensitive regions of the reaction profile where subtle changes to the dynamics of the active site can have an effect on the hydrogen and deuterium transfer process.     

Mediating electron transfer from bacteria to a gold electrode via a self-assembled monolayer

Numerous bacterial genera are known to respire anaerobically using macroscopic electrodes as electron acceptors. Typically, inexpensive graphite electrodes, which are readily colonized, are used to monitor electrogenic bacterial metabolism for microbial fuel cell and bioelectronics studies. We compare current production by electrogenic bacteria on gold electrodes coated with various alkanethiol self-assembled monolayers to current production on glassy carbon electrodes. Current production is correlated to chain length and headgroup of the monolayer molecules as expected. Relative to graphite, the coated gold electrodes achieve more reproducible experimental conditions and certain headgroups enhance electronic coupling to the bacteria.     

Ozone Decomposition Data for Kinetics Exercises

The goal of this paper is to provide data that can be used in a variety of exercises ranging from kinetics in general chemistry to advanced problems in physical chemistry. The data provided relates to ozone-decay kinetics in various atmospheres (O₂, N₂, Ar) as measured by ultraviolet/visible absorbance spectroscopy (UV/vis) at 254 nm. The absorbance of ozone is monitored over a 75-min time period, and by using Beers law the concentration is calculated. Nine data sets, each repeated three times, of absorbance measurements are provided for student exercises, and prelaboratory and postlaboratory questions are suggested.     

Vortex shedding from two finite circular cylinders in a staggered configuration

Wind tunnel experiments were conducted to measure the vortex shedding frequencies for two circular cylinders of finite height arranged in a staggered configuration. The cylinders were mounted normal to a ground plane and were partially immersed in a flat-plate turbulent boundary layer. The Reynolds number based on the cylinder diameter was Re_D=2.4×10⁴, the cylinder aspect ratio was AR=9, the boundary layer thickness relative to the cylinder height was δ/H=0.4, the centre-to-centre pitch ratio was varied from P/D=1.125 to 5, and the incidence angle was incremented in small steps from α=0° to 90°. The Strouhal numbers were obtained behind the upstream and downstream cylinders using hot-wire anemometry. From the behaviour of the Strouhal number data obtained at the mid-height position, the staggered configuration could be broadly classified by the pitch ratio as closely spaced (P/D<1.5), moderately spaced (1.5?P/D?3), or widely spaced (P/D>3). The closely spaced staggered finite cylinders were characterized by the same Strouhal number measured behind both cylinders, an indication of single bluff-body behaviour. Moderately spaced staggered finite cylinders were characterized by two Strouhal numbers at most incidence angles. Widely spaced staggered cylinders were characterized by a single Strouhal number for both cylinders, indicative of synchronized vortex shedding from both cylinders at all incidence angles. For selected staggered configurations representative of closely spaced, moderately spaced, or widely spaced behaviour, Strouhal number measurements were also made along the vertical lengths of the cylinders, from the ground plane to the free end. The power spectra showed that for certain cylinder arrangements, because of the influences of the cylinder–wall junction and free-end flow fields, the Strouhal numbers and flow patterns change along the cylinder.     

Polyamide resin: A novel immunoadsorbent

A solid phase assay for radiolabeled antibody synthesizedde novo in vitro has been described (1). The solid phase consists of antigen covalently bound to bromacetyl cellulose, a useful but difficult to prepare immunoadsorbent. Herein, we describe the preparation of polyamide resin immunoadsorbent and the procedure for coupling antigen to the polymer. Data are presented that show that polyamide resin-Ag? conjugates can replace bromacetyl cellulose-Ag conjugates. The usefulness of this easily prepared and inexpensive immunoadsorbent is discussed.     

Lifetime measurement in the β system (c1Φ-a1Δ) of TiO

The radiative lifetime of the v′ = 0 level of the c¹Φ state of TiO has been measured from observations on fluorescent decay of a single rotational level, following excitation by laser radiation. The value is τ₀ = 17.5 ± 1.0 nsec. From this is derived a transition probability of 5.71 × 10⁷ sec^?1 and an emission f value of 0.270. Transition probabilities for the other bands in the β system have been calculated.     

The temporal representation of speech in a nonlinear model of the guinea pig cochlea

The temporal representation of speechlike stimuli in the auditory-nerve output of a guinea pig cochlea model is described. The model consists of a bank of dual resonance nonlinear filters that simulate the vibratory response of the basilar membrane followed by a model of the inner hair cell/auditory nerve complex. The model is evaluated by comparing its output with published physiological auditory nerve data in response to single and double vowels. The evaluation includes analyses of individual fibers, as well as ensemble responses over a wide range of best frequencies. In all cases the model response closely follows the patterns in the physiological data, particularly the tendency for the temporal firing pattern of each fiber to represent the frequency of a nearby formant of the speech sound. In the model this behavior is largely a consequence of filter shapes; nonlinear filtering has only a small contribution at low frequencies. The guinea pig cochlear model produces a useful simulation of the measured physiological response to simple speech sounds and is therefore suitable for use in more advanced applications including attempts to generalize these principles to the response of human auditory system, both normal and impaired.