Distance Dependence of Electron Transfer Kinetics for Azurin Protein Adsorbed to Monolayer Protected Nanoparticle Film Assemblies

The distance dependence and kinetics of the heterogeneous electron transfer (ET) reaction for the redox protein azurin adsorbed to an electrode modified with a gold nanoparticle film are investigated using cyclic voltammetry. The nanoparticle films are comprised of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), which are covalently networked with dithiol linkers. The MPC film assembly serves as an alternative adsorption platform to the traditional alkanethiolate self-assembled monolayer (SAM) modified electrodes that are commonly employed to study the ET kinetics of immobilized redox proteins, a strategy known as protein monolayer electrochemistry. Voltammetric analysis of the ET kinetics for azurin adsorbed to SAMs of increasing chain length results in quasi-reversible voltammetry with significant peak splitting. We observed rate constants (k°ET) of 12−20 s−1 for the protein at SAMs of shorter alkanethiolates that decays exponentially (β = 0.9/CH2 or 0.8/Å) at SAMs of longer alkanethiolates (9−11 methylene units) or an estimated distance of 1.23 nm and is representative of classical electronic tunneling behavior over increasing distance. Azurin adsorbed to the MPC film platforms of increasing thickness results in reversible voltammetry with very little voltammetric peaks splitting and nearly negligible decay of the ET rate over significant distances up to 20 nm. The apparent lack of distance dependence for heterogeneous ET reactions at MPC film assemblies is attributed to a two-step mechanism involving extremely fast electronic hopping through the MPC film architecture. These results suggest that MPC platforms may be used in protein monolayer electrochemistry to create adsorption platforms of higher architecture that can accommodate greater than monolayer protein coverage and increase the Faradaic signal, a finding with significant implications for amperometric biosensor design and development

Monte-Carlo calculation of longitudinal and transverse resistivities in a model Type-II superconductor

We study the effect of a transport current on the vortex-line lattice in isotropic type-II superconductors in the presence of strong thermal fluctuations by means of 'driven-diffusion' Monte Carlo simulations of a discretized London theory with finite magnetic penetration depth. We calculate the current-voltage (I-V) characteristics for various temperatures, for transverse as well as longitudinal currents I. From these characteristics, we estimate the linear resistivities R_xx=R_yy and R_zz and compare these with equilibrium results for the vortex-lattice structure factor and the helicity moduli. From this comparison a consistent picture arises, in which the melting of the flux-line lattice occurs in two stages for the system size considered. In the first stage of the melting, at a temperature T_m, the structure factor drops to zero and R_xx becomes finite. For a higher temperature T_z, the second stage takes place, in which the longitudinal superconducting coherence is lost, and R_zz becomes finite as well. We compare our results with related recent numerical work and experiments on cuprate superconductors.Comment: 4 pages, with eps figure

Evolution of Asthma Severity in a Cohort of Young Adults: Is There Any Gender Difference?

INTRODUCTION:Little is known about the distribution of asthma severity in men and women in the general population. The objective of our study was to describe asthma severity and change in severity according to gender in a cohort of adult asthmatics METHODS:Subjects with asthma were identified from random samples of the 22 to 44 year-olds from the general population, screened for asthma from 1991 to 1993 in 48 centers from 22 countries and followed-up during 1998-2002, as part of the European Community Respiratory Health Survey (ECRHS). All participants to follow-up with current asthma at baseline were eligible for the analysis. To assess change over the follow-up, asthma severity at the two surveys was defined using standardized data on respiratory symptoms, lung function and medication according to the Global Initiative for Asthma (GINA) Guidelines. Another quantitative score (Ronchetti) further considering hospitalizations was also analysed. RESULTS:The study included 685 subjects with asthma followed-up over a mean period of 8.65 yr (min 4.3-max 11.7). At baseline, asthma severity according to GINA was distributed as intermittent: 40.7%, 31.7% as mild persistent, 14% as moderate persistent, and 13.5% as severe persistent. Using the Ronchetti score derived classification, the distribution of asthma severity was 58% mild, (intermittent and mild persistent), 25.8% moderate, and 15.4% severe. Whatever the classification, there was no significant difference in the severity distribution between men and women. There was also no gender difference in the severity distribution among incident cases which developed asthma between the two surveys. Men with moderate-to-severe asthma at baseline were more likely than women to have moderate-to-severe asthma at follow-up. Using GINA, 69.2% of men vs. 53.1% of women (p = 0.09) with moderate-to-severe asthma at baseline were still moderate-to-severe at follow-up. Using Ronchetti score, 53.3% of men vs. 36.2% of women (p = 0.03) with moderate-to-severe asthma at baseline were still moderate-to-severe at follow-up. CONCLUSIONS:There was no gender difference in asthma severity at the two surveys. However, our findings suggest that asthma severity might be less stable in women than in men

Development of CVD diamond radiation detectors

Diamond is a nearly ideal material for detecting ionizing radiation. Its outstanding radiation hardness, fast charge collection and low leakage current allow a diamond detector to be used in high ra diation, high temperature and in aggressive chemical media. We have constructed charged particle detectors using high quality CVD diamond. Characterization of the diamond samples and various detect ors are presented in terms of collection distance, $d=\mu E \tau$, the average distance electron-hole pairs move apart under the influence of an electric field, where $\mu$ is the sum of carrier mo bilities, $E$ is the applied electric field, and $\tau$ is the mobility weighted carrier lifetime. Over the last two years the collection distance increased from $\sim$ 75 $\mu$m to over 200 $\mu$ m. With this high quality CVD diamond a series of micro-strip and pixel particle detectors have been constructed. These devices were tested to determine their position resolution and signal to n oise performance. Diamond detectors were exposed to large fluences of pions, protons and neutrons to establish their radiation hardness properties. The results of these tests and their correlati on with the characterization studies are presented

Proton Irradiation of CVD Diamond Detectors for High Luminosity Experiments at the LHC

CVD diamond shows promising properties for use as a position sensitive detector for experiments in the highest radiation areas at the Large Hadron Collider. In order to study the radiation hardn ess of diamond we exposed CVD diamond detector samples to 24~GeV/$c$ and 500~MeV protons up to a fluence of $5\times 10^{15}~p/{\rm cm^2}$. We measured the charge collection distance, the ave rage distance electron hole pairs move apart in an external electric field, and leakage currents before, during, and after irradiation. The charge collection distance remains unchanged up to $1\ times 10^{15}~p/{\rm cm^2}$ and decreases by $\approx$40~\% at $5\times 10^{15}~p/{\rm cm^2}$. Leakage currents of diamond samples were below 1~pA before and after irradiation. The particle indu ced currents during irradiation correlate well with the proton flux. In contrast to diamond, a silicon diode, which was irradiated for comparison, shows the known large increase in leakage curren t. We conclude that CVD diamond detectors are radiation hard to 24~GeV/$c$ and 500~MeV protons up to at least $1\times 10^{15}~p/{\rm cm^2}$ without signal loss