Information guided noise reduction for Monte Carlo integration of oscillatory functions

A simple procedure for decreasing the statistical error associated with Monte Carlo integration of oscillatory functions is presented. The method uses available information about the integral of a similar oscillatory function to correlate the estimates of the positive and negative components of the integral. Numerical tests show that information guided noise reduction (IGNoR) leads to substantial decrease of the statistical error, allowing meaningful results to be obtained with a fraction of the cost required to attain similar precision from the raw Monte Carlo estimate.     

Optimization of separations of alkyl-substituted phenolate anions by capillary zone electrophoresis

Anions of alkylphenols have very similar electrophoretic mobilities in CZE owing to their very small differences in size and the narrow range of their pK_a values. By studying electrophoretic mobility as a function both of pH and of the amount of acetonitrile in the electrolyte solution, optimum separation conditions were determined. It was possible to separate a group of methyl-substituted phenols, including several positional isomers. Mixtures containing n-propyl and isopropyl phenols and 1°, 2°, and 3° butylphenols could be resolved.     

A network-related nuclear power plant model with an intelligent branch-and-bound solution approach

This paper presents a network model with discrete requirements for a nuclear power plant. The model determines the batch size and timing for nuclear unit refueling and how much energy should be produced by nuclear and non-nuclear units for each time period to satisfy forecasted demand with minimum total operating costs over the planning horizon. Efficient modeling and solution strategies are developed which constitute a merger of operations research and artificial intelligence. A branch-and-bound solution approach is combined with a pattern recognition component, involving non-parametric discrimination analyses, to select branching variables and directions. By coupling this approach with network optimization techniques to exploit the underlying network structure of the problem, substantial improvements are obtained both in solution quality and solution efficiency.This research was supported in part by the Center for Business Decision Analysis, the Hugh Roy Cullen Centennial Chair in Business Administration, and the Office of Naval Research under contract N00014-87-K-0190. Reproduction in whole or in part is permitted for any purpose of the U.S. Government. CENTER FOR BUSINESS DECISION ANALYSIS Darwin Klingman, Director The University of Texas at Austin Austin, TX 78712, U.S.A.     

Shock Tube Measurements of the Rate Constant of the Reaction NCN + O2

The rate constant of the comparably slow bimolecular NCN radical reaction NCN + O₂ has been measured for the first time under combustion relevant conditions using the shock tube method. The thermal decomposition of cyanogen azide (NCN₃) served as a clean high‐temperature source of NCN radicals. NCN concentration–time profiles have been detected by narrow‐bandwidth laser absorption at cm^?1. The experiments behind incident shock waves have been performed with up to 17% O₂ in the reaction gas mixture. At such high O₂ mole fractions, it was necessary to take O₂ relaxation into account that caused a gradual decrease of the temperature during the experiment. Moreover, following fast decomposition of NCN₃ and collision‐induced intersystem crossing of the initially formed singlet NCN to its triplet ground state, an unexpected and slow additional formation of triplet NCN has been observed on a 100‐μs timescale. This delayed NCN formation was attributed to a fast recombination of ¹NCN with O₂ forming a ³NCNOO adduct acting as a reservoir species for NCN. Rate constant data for the reaction NCN + O₂ have been measured at temperatures between 1674 and 2308 K. They are best represented by the Arrhenius expression . No pressure dependence has been observed at pressures between 216 and 706 mbar.     

Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues

Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans‐2,6‐dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two‐step trans arylation of AR products to access 2,6‐trans‐dihydropyranones. This new trans‐arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier‐type and Tsuji–Trost‐type reactions, was finally enabled by an unprecedented, highly regioselective γ‐deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck–Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (?)‐musellarins A–C and 12 analogues in 11–12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three‐to‐six times greater potency than the musellarins as promising new leads.     

Pre-averaged kernel estimators for the drift function of a diffusion process in the presence of microstructure noise

We consider estimation of the drift function of a stationary diffusion process when we observe high-frequency data with microstructure noise over a long time interval. We propose to estimate the drift function at a point by a Nadaraya–Watson estimator that uses observations that have been pre-averaged to reduce the noise. We give conditions under which our estimator is consistent and asympotically normal. Its rate and asymptotic bias and variance are the same as those without microstructure noise. To use our method in data analysis, we propose a data-based cross-validation method to determine the bandwidth in the Nadaraya–Watson estimator. Via simulation, we study several methods of bandwidth choices, and compare our estimator to several existing estimators. In terms of mean squared error, our new estimator outperforms existing estimators.     

A parametric study of laser induced thin film spallation

We report parametric studies of elastic wave generation by a pulsed laser and associated spalling of thin surface films by the corresponding high stresses. Two different substrate materials, single crystal Si (100) and fused silica, are considered. Spallation behavior of Al thin films is investigated as a function of substrate thickness, film thickness, laser energy, and various parameters governing the source. Surface displacement due to the stress wave is measured by Michaelson interferometry and used to infer the stresses on the film interface. Consistent with previous studies, the maximum stress in the substrate and at the film/substrate interface increases with increasing laser fluence. For many of the conditions tested, the substrate stress is large enough to damage the Si. Moreover, the maximum interface stress is found to increase with increasing film thickness, but decrease with increasing substrate thickness due to geometric attenuation. Of particular significance is the development of a decompression shock in the fused sillica substrates, which results in very high tensile stresses at the interface. This shock enhances the failure of thin film interfaces, especially in thicker samples.     

Genetics in primary care: a USA faculty development initiative

The Genetics in Primary Care (GPC) project is a USA national faculty development initiative with the goal of enhancing the training of medical students and primary care residents by developing primary care faculty expertise in genetics. Educational strategies were developed for the project by an executive committee with input from an advisory committee, comprising individuals with primary care, medical education and genetics expertise. These committees identified the key issues in genetics education for primary care as (1) considering inherited disease in the differential diagnosis of common disorders; (2) using appropriate counseling strategies for genetic testing and diagnosis, and (3) understanding the implications of a genetic diagnosis for family members. The group emphasized the importance of a primary care perspective, which suggests that the clinical utility of genetic information is greatest when it has the potential to improve health outcomes. The group also noted that clinical practice already incorporates the use of family history information, providing a basis for discussing the application of genetic concepts in primary care. Genetics and primary care experts agreed that educational efforts will be most successful if they are integrated into existing primary care teaching programs, and use a case-based teaching format that incorporates both clinical and social dimensions of genetic disorders. Three core clinical skills were identified: (1) interpreting family history; (2) recognizing the variable clinical utility of genetic information, and (3) acquiring cultural competency. Three areas of potential controversy were identified as well: (1) the role of nondirective counseling versus shared decision-making in discussions of genetic testing; (2) the intrinsic value of genetic information when it does not influence health outcomes, and (3) indications for a genetics referral. The project provides an opportunity for ongoing discussion about these important issues.