Low Temperature Photo-oxidation of Chloroperoxidase Compound II

Oxidation of the heme-thiolate enzyme chloroperoxidase (CPO) from Caldariomyces fumago with peroxynitrite (PN) gave the Compound II intermediate, which was photo-oxidized with 365 nm light to give a reactive oxidizing species. Cryo-solvents at pH ≈ 6 were employed, and reactions were conducted at temperatures as low as − 50 °C. The activity of CPO as evaluated by the chlorodimedone assay was unaltered by treatment with PN or by production of the oxidizing transient and subsequent reaction with styrene. EPR spectra at 77 K gave the amount of ferric protein at each stage in the reaction sequence. The PN oxidation step gave a 6:1 mixture of Compound II and ferric CPO, the photolysis step gave an approximate 1:1 mixture of active oxidant and ferric CPO, and the final mixture after reaction with excess styrene contained ferric CPO in 80% yield. In single turnover reactions at − 50 °C, styrene was oxidized to styrene oxide in high yield. Kinetic studies of styrene oxidation at − 50 °C displayed saturation kinetics with an equilibrium constant for formation of the complex of Kbind = 3.8 × 104 M− 1 and an oxidation rate constant of kox = 0.30 s− 1. UV–Visible spectra of mixtures formed in the photo-oxidation sequence at ca. − 50 °C did not contain the signature Q-band absorbance at 690 nm ascribed to CPO Compound I prepared by chemical oxidation of the enzyme, indicating that different species were formed in the chemical oxidation and the photo-oxidation sequence

Parameter Estimation of Actuators for Benchmark Active Control Technology (BACT) Wind Tunnel Model with Analysis of Wear and Aerodynamic Loading Effects

This report describes the development of transfer function models for the trailing-edge and upper and lower spoiler actuators of the Benchmark Active Control Technology (BACT) wind tunnel model for application to control system analysis and design. A simple nonlinear least-squares parameter estimation approach is applied to determine transfer function parameters from frequency response data. Unconstrained quasi-Newton minimization of weighted frequency response error was employed to estimate the transfer function parameters. An analysis of the behavior of the actuators over time to assess the effects of wear and aerodynamic load by using the transfer function models is also presented. The frequency responses indicate consistent actuator behavior throughout the wind tunnel test and only slight degradation in effectiveness due to aerodynamic hinge loading. The resulting actuator models have been used in design, analysis, and simulation of controllers for the BACT to successfully suppress flutter over a wide range of conditions

Factors associated with invasive lung aspergillosis and the significance of positive aspergillus culture after liver transplantation

From January 1981 to December 1990, 2180 patients underwent orthotopic liver transplantation at the University of Pittsburgh. Thirty-two patients (1.5%) were identified with invasive aspergillosis (29 lung, 2 intraabdominal, 1 meningitis). Of 29 patients with invasive lung disease, only 23 (79%) had positive culture (Aspergillus fumigatus, 20; Aspergillus flavus, 3). Forty-eight variables were analyzed and compared in 23 patients with invasive disease with positive cultures and 9 patients with colonization only. The variables associated with pulmonary invasive disease, by univariate analysis, were surgical time (P =.03), presence of laparotomies (P =.02), higher creatinine level at time of Aspergillus isolation (P =.01), and use of OKT3 (P =.02). However, in a multivariate analysis, only the last two (creatinine, OKT3) were associated with invasive lung aspergillosis. Of 4 patients with positive abdominal wound culture, 2 had local invasive aspergillosis. Therefore, positive cultures of Aspergillus organisms from respiratory secretions and wound drainage may represent invasive disease and should not be ignored. © 1992 the University of Chicago

Daily Sleep Quality is Associated with Daily Cognition in Late-Life

Background: Older adults often face sleep disturbance or cognitive decline that goes beyond the scope of normal aging. The present study examined the relationship between self-reported sleep quality and self-reported daytime attention in a community-dwelling sample of older men at the between-persons and within-persons levels of association. Methods: Thirty-eight participants (M age =75.36 years, SD age =7.51 years, range=66-90 years) completed a twice-daily sleep diary for one week. Sleep quality and attention were assessed using a single-item 0-10 rating scales from the morning diary (“How was the quality of your sleep last night?”) and from the evening diary (“How was your attention today?”). A two-level multilevel model was parameterized with days nested within individuals to examine whether nightly sleep quality predicts an individual’s daily attention rating. Results: A multilevel model predicting self-reported attention revealed (1) older individuals who reported better sleep quality reported having better daily attention [Beta=0.64, t(248.15)=10.12, p\u3c0.001] and (2) following a day of above-average sleep quality, older individuals experienced above-average attention [Beta=0.16, t(259.79)=2.75, p=.006]. Conclusion: Not only was overall sleep quality associated with self-reported attention, but a good night\u27s sleep was associated with better self-reported next-day attention. Results point to the potential importance of fluctuations in sleep quality for daytime functioning. Interventions aimed at improving nightly sleep consistency may be worth exploring as methods to improve daytime cognitive functioning in older adults. Support: This work was supported by the Sleep Research Society Foundation/Jazz Pharmaceuticals (001JP13, PI: Dzierzewski) and by the National Institute on Aging of the National Institutes of Health under Award Number K23AG049955 (PI: Dzierzewski), and National Heart Lung and Blood Institute at the National Institutes of Health under award number K24HL143055 (PI: Martin). The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health or the Department of Veterans Affairs.https://scholarscompass.vcu.edu/gradposters/1089/thumbnail.jp

Influence of rivet to sheet edge distance on fatigue strength of self-piercing riveted aluminium joints

Self-piercing riveting (SPR) is one of the main joining methods for lightweight aluminium automotive body structures due to its advantages. In order to further optimise the structure design and reduce the weight but without compromising strength, reduction of redundant materials in the joint flange area can be considered. For this reason, the influence of rivet to sheet edge distance on the fatigue strengths of self-piercing riveted joints was studied. Five edge distances, 5 mm, 6 mm, 8 mm, 11.5 mm and 14.5 mm, were considered. The results showed that the SPR joints studied in this research had high fatigue resistance and all specimens failed in sheet material along joint buttons or next to rivet heads. For lap shear fatigue tests, specimens failed in the bottom sheet at low load amplitudes and in the top sheet at high load amplitudes except for specimens with very short edge distance of 5 and 6 mm; whereas, for coach-peel fatigue tests, all specimens failed in the top sheet. For both lap shear and coach-peel fatigue tests, specimens with an edge distance of 11.5 mm had the best fatigue resistance. It was found that for coach-peel fatigue, length of crack developing path before specimens lost their strengths was the main factor that determined the fatigue life of different specimens; for lap shear fatigue, the level of stress concentration and subsequent crack initiation time was the main factor that determined the fatigue life

Optimization Of Photobioreactor For Astaxanthin Production In Chlorella Zofingiensis.

Master'sMASTER OF ENGINEERIN