Assessing Internal Audit Quality

Internal audit quality is an issue of great importance to both the internal and external audit professions. PCAOB Auditing Standard No 2 highlights this importance when addressing the reliance that the external auditor can place on the internal audit work product. The study discussed here experimentally tests the influence of the source of the internal audit function on both the internal and external auditors\u27 evaluation of the quality of the internal audit function. To assess the importance of the internal audit function\u27s sourcing arrangement in the internal audit function\u27s quality assessment, the researchers employ a case study approach, modifying a case that has been used in prior research. The researchers find that for three of the four measured internal audit function quality characteristics, there was no difference in the assessment of the internal audit function between internal and external auditors, regardless of whether or not the internal audit function was provided in-house or was outsourced to a CPA firm other than the external auditor\u27s firm

Lewis Acid Enhancement of Proton Induced CO_2 Cleavage: Bond Weakening and Ligand Residence Time Effects

Though Lewis acids (LAs) have been shown to have profound effects on carbon dioxide (CO_2) reduction catalysis, the underlying cause of the improved reactivity remains unclear. Herein, we report a well-defined molecular system for probing the role of LA additives in the reduction of CO_2 to carbon monoxide (CO) and water. Mo(0) CO_2 complex (2) forms adducts with a series of LAs, demonstrating CO_2 activation that correlates linearly with the strength of the LA. Protons induce C–O cleavage of these LA adducts, in contrast to the CO_2 displacement primarily observed in the absence of LA. CO_2 cleavage shows dependence on both bond activation and the residence time of the bound small molecule, demonstrating the influence of both kinetic and thermodynamic factors on promoting productive CO_2 reduction chemistry

A Comparison of the Performance of African American Preschool Children on the WPPSI and WPPSI-R

The Wechsler Preschool and Primary Scale of Intelligence (WPPSI) (Wechsler, 1967) has long been one of the most widely used instruments for the assessment of preschool children\u27s intelligence. The recently published Wechsler Preschool and Primary Scale of Intelligence Revised (WPPSI-R) (Wechsler, 1989) was designed to replace the WPPSI as the instrument of choice for the purposes of making classification, placement, and program evaluation decisions. Thus, data concerning the comparability of the two instruments is of particular importance to educators. This study investigated the relationship between the WPPSI and the WPPSI-R among a sample of predominantly lower socioeconomic status African American children in order to afford some estimate of the relative similarities or differences that might exist between the two instruments. Twenty-four African American children ages four and five were administered the WPPSI and the WPPSI-R in counterbalanced order. Group mean scores on the individual subtests and on the Verbal, Performance, and Full Scales of the two instruments were compared. Results indicated that scores on the WPPSI were consistently higher than were those on the WPPSI-R. Differences between the two tests were 8.3, 13.6, and 11.7 in favor of the WPPSI for the Verbal, Performance, and Full Scale IQs, respectively. Data from this study support the view that population gains in IQ scores are occurring at the lower socioeconomic strata. The practical implications of changes in IQ scores due to the re-norming of the WPPSI-R are discussed

Surface Roughness Parameter Uncertainties on Radar Based Soil Moisture Retrievals

Surface roughness variations are often assumed to be negligible for the retrieval of sol moisture. Although previous investigations have suggested that this assumption is reasonable for natural vegetation covers (i.e. Moran et al. 2002), in-situ measurements over plowed agricultural fields (i.e. Callens et al. 2006) have shown that the soil surface roughness can change considerably due to weathering induced by rain

Application of the Tor Vergata Scattering Model to L Band Backscatter During the Corn Growth Cycle

At the USDA's Optimizing Production Inputs for Economic and Environmental Enhancement (OPE3) experimental site in Beltsville, Maryland, USA) a field campaign took place throughout the 2002 corn growth cycle from May 10th (emergence of corn crops) to October 2nd (harvest). One of the microwave instruments deployed was the multi-frequency (X-, C- and L-band) quad-polarized (HH, HV, VV, VH) NASA GSFC/George Washington University (GWU) truck mounted radar. During the field campaign, this radar system provided once a week fully polarized C- and L-band (4.75 and 1.6 GHz) backscatter measurements from incidence angle of 15, 35, and 55 degrees. In support of microwave observations, an extensive ground characterization took place, which included measurements of surface roughness, soil moisture, vegetation biomass and morphology. The field conditions during the campaign are characterized by several dry downs with a period of drought in the month of August. Peak biomass the corn canopies was reached on July 24th with a total biomass of approximately 6.5 kg/sq m. This dynamic range in both soil moisture and vegetation conditions within the data set is ideal for the validation of discrete medium vegetation scattering models. In this study, we compare the L band backscatter measurements with simulations by the Tor Vergata model (ferrazzoli and Guerriero 1996). The measured soil moisture, vegetation biomass and most reliably measured vegetation morphological parameters (e.g. number of leaves, number of stems and stem height) were used as input for the Tor Vergata model. The more uncertain model parameters (e.g. surface roughness, leaf thickness) and the stem diameter were optimized using a parameter estimation routine based on the Levenberg-Marquardt algorithm. As cost function for this optimization, the HH and VV polarized backscatter measured and stimulated by the TOR Vergata model for incidence angle of 15, 35, and 55 degrees were used (6 measurements in total). The calibrated Tor Vergata model simulations are in excellent agreement with the measurements of Root Mean Squared Differences (RMSD's) of 0.8, 0.9 and 1.4 dB for incidences of 15, 35 and 55 degrees, respectively. The results from this study that a physically based scattering model with the appropriate parameterization can accurately simulate backscatter measurements and, as such, have the potential of being used for the retrieval of biophysical variables (e.g. soil moisture and vegetation biomass)

CO Coupling Chemistry of a Terminal Mo Carbide: Sequential Addition of Proton, Hydride, and CO Releases Ethenone

The mechanism originally proposed by Fischer and Tropsch for carbon monoxide (CO) hydrogenative catenation involves C–C coupling from a carbide-derived surface methylidene. A single molecular system capable of capturing these complex chemical steps is hitherto unknown. Herein, we demonstrate the sequential addition of proton and hydride to a terminal Mo carbide derived from CO. The resulting anionic methylidene couples with CO (1 atm) at low temperature (−78 °C) to release ethenone. Importantly, the synchronized delivery of two reducing equivalents and an electrophile, in the form of a hydride (H– = 2e– + H+), promotes alkylidene formation from the carbyne precursor and enables coupling chemistry, under conditions milder than those previously described with strong one-electron reductants and electrophiles. Thermodynamic measurements bracket the hydricity and acidity requirements for promoting methylidene formation from carbide as energetically viable relative to the heterolytic cleavage of H2. Methylidene formation prior to C–C coupling proves critical for organic product release, as evidenced by direct carbide carbonylation experiments. Spectroscopic studies, a monosilylated model system, and Quantum Mechanics computations provide insight into the mechanistic details of this reaction sequence, which serves as a rare model of the initial stages of the Fischer–Tropsch synthesis

S-wave/spin-triplet order in superconductors without inversion symmetry: Li2_2Pd3_3B and Li2_2Pt3_3B

We investigate the order parameter of noncentrosymmetric superconductors Li$_2$Pd$_3$B and Li$_2$Pt$_3$B via the behavior of the penetration depth $\lambda(T)$. The low-temperature penetration depth shows BCS-like behavior in Li$_2$Pd$_3$B, while in Li$_2$Pt$_3$B it follows a linear temperature dependence. We propose that broken inversion symmetry and the accompanying antisymmetric spin-orbit coupling, which admix spin-singlet and spin-triplet pairing, are responsible for this behavior. The triplet contribution is weak in Li$_2$Pd$_3$B, leading to a wholly open but anisotropic gap. The significantly larger spin-orbit coupling in Li$_2$Pt$_3$B allows the spin-triplet component to be larger in Li$_2$Pt$_3$B, producing line nodes in the energy gap as evidenced by the linear temperature dependence of $\lambda(T)$. The experimental data are in quantitative agreement with theory.Comment: Phys. Rev. Lett. (in press). More details are include

Total Synthesis and Characterization of 7-Hypoquinuclidonium Tetrafluoroborate and 7-Hypoquinuclidone BF_3 Complex

Derivatives of the fully twisted bicyclic amide 7-hypoquinuclidone are synthesized using a Schmidt–Aubé reaction. Their structures were unambiguously confirmed by X-ray diffraction analysis and extensive spectroscopic characterization. Furthermore, the stability and chemical reactivity of these anti-Bredt amides are investigated. 7-Hypoquinuclidonium tetrafluoroborate is shown to decompose to a unique nitrogen bound amide–BF_3 complex of 7-hypoquinuclidone under anhydrous conditions and to react instantaneously with water making it one of the most reactive amides known to date

Effects of Geochemical and Environmental Parameters on Abiotic Organic Chemistry Driven by Iron Hydroxide Minerals

Geological conditions play a significant role in prebiotic/abiotic organic chemistry, especially when reactive minerals are present. Previous studies of the prebiotic synthesis of amino acids and other products in mineral‐containing systems have shown that a diverse array of compounds can be produced, depending on the experimental conditions. However, these previous experiments have not simulated the effects of varying geochemical conditions, in which factors such as pH, iron redox state, or chemical concentrations may vary over time and space in a natural environment. In geochemical systems that contain overlapping gradients, many permutations of individual conditions could exist and affect the outcome of an organic reaction network. We investigated reactions of pyruvate and glyoxylate, two compounds that are central to the emergence of metabolism, in simulated geological gradients of redox, pH, and ammonia concentration. Our results show that the positioning of pyruvate/glyoxylate reactions in this environmental parameter space determines the organic product distribution that results. Therefore, the distribution pattern of amino acids and alpha‐hydroxy acids produced prebiotically in a system reflects the specific reaction conditions, and would be distinct at various locations in an environment depending on local geochemistry. This is significant for origin of life chemistry in which the composition and function of oligomers could be affected by the environmentally driven distribution of monomers available. Also, for astrobiology and planetary science where organic distribution patterns are sometimes considered as a possible biosignature, it is important to consider environmentally driven abiotic organic reactions that might produce similar effects

Lewis Acid Enhancement of Proton Induced CO_2 Cleavage: Bond Weakening and Ligand Residence Time Effects

Though Lewis acids (LAs) have been shown to have profound effects on carbon dioxide (CO_2) reduction catalysis, the underlying cause of the improved reactivity remains unclear. Herein, we report a well-defined molecular system for probing the role of LA additives in the reduction of CO_2 to carbon monoxide (CO) and water. Mo(0) CO_2 complex (2) forms adducts with a series of LAs, demonstrating CO_2 activation that correlates linearly with the strength of the LA. Protons induce C–O cleavage of these LA adducts, in contrast to the CO_2 displacement primarily observed in the absence of LA. CO_2 cleavage shows dependence on both bond activation and the residence time of the bound small molecule, demonstrating the influence of both kinetic and thermodynamic factors on promoting productive CO_2 reduction chemistry