The Operational Audit: A Business Appraisal Approach to Improved Operations and Profitability

The operational audit is concerned with the appraisal of company effectiveness, identifying operations which are open to improvement. This paper looks at the history of the operational audit and its relationship to other types of audit. The scope of the operational audit is discussed and so also is the manner in which assignments are typically conducted. Two case studies, one in a sales company and the other in a production company, are presented, and details are provided of the results obtained. The relationship of operational research to operational audit is reviewed, and the benefits of including operational researchers in audit teams are pointed out.     

OH-stretch vibrational spectroscopy of hydroxymethyl hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH(2)OOH) and its partially deuterated analogue, HOCD(2)OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1nu(OH) and 2nu(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH(2)OOH initiated by excitation of the 4nu(OH) and 5nu(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4nu(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.     

Raman and surface‐enhanced Raman spectroscopic studies of the 15‐mer DNA thrombin‐binding aptamer

Aptamers are single‐stranded oligonucleotides that selectively bind to their target molecules owing to their ability to form secondary structures and shapes. The 15‐mer (5′‐GGTTGGTGTGGTTGG‐3′) DNA thrombin‐binding aptamer (TBA) binds to thrombin following the formation of a quadruplex structure via the Hoogsten‐type G–G interactions. In the present study, Raman and SERS spectra of TBA and thiolated TBA (used to facilitate covalent bonding to metal nanoparticle) in different conditions are investigated. The spectra of the two analogs exhibit vibrations, such as the C8N7 H2 deformation band at ∼1480 cm⁻¹ of the guanine tetrad, that are characteristic of the quadruplex structure in the presence of K⁺ ions or at low temperature. Interestingly, SERS spectra of the two analogs differ markedly from their respective normal Raman spectra, possibly due to changes in the conformation of the aptamer upon binding, as well as to the specific interaction of individual vibrational modes with the metal surface. In addition, the SERS spectra of the thiolated aptamer show significant changes with different concentrations, which may be due to different orientation of the molecule with respect to the metal surface. This study provides useful information for the development of label‐free aptamer‐based SERS sensors and assays. Copyright © 2009 John Wiley & Sons, Ltd.     

DICE: exploiting <Emphasis Type="Italic">all</Emphasis> bivariate dependencies in binary and multary search spaces

Although some of the earliest Estimation of Distribution Algorithms (EDAs) utilized bivariate marginal distribution models, up to now, all discrete bivariate EDAs had one serious limitation: they were constrained to exploiting only a limited O(d) subset out of all possible \(O(d^{2})\) bivariate dependencies. As a first we present a family of discrete bivariate EDAs that can learn and exploit all \(O(d^{2})\) dependencies between variables, and yet have the same run-time complexity as their more limited counterparts. This family of algorithms, which we label DICE (DIscrete Correlated Estimation of distribution algorithms), is rigorously based on sound statistical principles, and particularly on a modelling technique from statistical physics: dichotomised multivariate Gaussian distributions. Initially (Lane et al. in European Conference on the Applications of Evolutionary Computation, Springer, 1999), DICE was trialled on a suite of combinatorial optimization problems over binary search spaces. Our proposed dichotomised Gaussian (DG) model in DICE significantly outperformed existing discrete bivariate EDAs; crucially, the performance gap increasingly widened as dimensionality of the problems increased. In this comprehensive treatment, we generalise DICE by successfully extending it to multary search spaces that also allow for categorical variables. Because correlation is not wholly meaningful for categorical variables, interactions between such variables cannot be fully modelled by correlation-based approaches such as in the original formulation of DICE. Therefore, here we extend our original DG model to deal with such situations. We test DICE on a challenging test suite of combinatorial optimization problems, which are defined mostly on multary search spaces. While the two versions of DICE outperform each other on different problem instances, they both outperform all the state-of-the-art bivariate EDAs on almost all of the problem instances. This further illustrates that these innovative DICE methods constitute a significant step change in the domain of discrete bivariate EDAs.     

Catalytic C-H arylation of SEM-protected azoles with palladium complexes of NHCs and phosphines

[reaction: see text] The synthesis and catalytic evaluation of palladium complexes containing imidazolyl carbene ligand of varying steric and electronic properties is reported. These complexes catalyze the efficient C-H arylation of SEM-protected azole heteroarenes and thus provide a good method for preparation of a wide range of arylated free (NH)-azoles including pyrroles, indoles, imidazoles, and imidazo[1,2-a]pyridines. The reaction is operationally simple; the complexes are insensitive to moisture.     

Three hierarchies of simple games parameterized by “resource” parameters

This paper contributes to the program of numerical characterization and classification of simple games outlined in the classic monograph of von Neumann and Morgenstern. We suggest three possible ways to classify simple games beyond the classes of weighted and roughly weighted games. To this end we introduce three hierarchies of games and prove some relationships between their classes. We prove that our hierarchies are true (i.e., infinite) hierarchies. In particular, they are strict in the sense that more of the key “resource” (which may, for example, be the size or structure of the “tie-breaking” region where the weights of the different coalitions are considered so close that we are allowed to specify either winningness or nonwinningness of the coalition) yields the flexibility to capture strictly more games.     

Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions

Time‐resolved pump–probe gas‐phase X‐ray scattering signals, extrapolated to zero momentum transfer, provide a measure of the number of electrons in a system, an effect that arises from the coherent addition of elastic scattering from the electrons. This allows to identify reactive transients and determine the chemical reaction kinetics without the need for extensive scattering simulations or complicated inversion of scattering data. We examine the photodissociation reaction of trimethylamine and identify two reaction paths upon excitation to the 3p state at 200 nm: a fast dissociation path out of the 3p state to the dimethyl amine radical (16.6±1.2 %) and a slower dissociation via internal conversion to the 3s state (83.4±1.2 %). The time constants for the two reactions are 640±130 fs and 74±6 ps, respectively. Additionally, it is found that the transient dimethyl amine radical has a N?C bond length of 1.45±0.02 Å and a C?N?C bond angle of 118°±4°.     

High-spin isomers in Rn in the region of triple neutron core-excitations

The level scheme of ²¹²Rn has been extended to spins of ∼38?$\sim 38?$ and excitation energies of about 13 MeV using the ²⁰⁴Hg(¹³C, 5n)²¹²Rn reaction and γ-ray spectroscopy. Time correlated techniques have been used to obtain sensitivity to weak transitions and channel selectivity. The excitation energy of the 22⁺ core-excited isomer has been established at 6174 keV. Two isomers with τ=25(2) ns$\tau =25(2)\text{ns}$ and τ=12(2) ns$\tau =12(2)\text{ns}$ are identified at 12211 and 12548 keV, respectively. These are the highest-spin nuclear isomers now known, and are attributed to configurations involving triple neutron core-excitations coupled to the aligned valence protons. Semi-empirical shell-model calculations can account for most states observed, but with significant energy discrepancies for some configurations.