A Comparative Review of Computational Methods as Applied to Gold(I) Complexes and Mechanisms

In the last two decades, the field of homogeneous gold catalysis has been

extremely active, growing at a rapid pace. Another rapidly-growing field—that of

computational chemistry—has often been applied to the investigation of various gold-

catalyzed reaction mechanisms. Unfortunately, a number of recent mechanistic studies

have utilized computational methods that have been shown to be inappropriate and

inaccurate in their description of gold chemistry. This work presents an overview of

available computational methods with a focus on the approximations and limitations

inherent in each, and offers a review of experimentally-characterized gold(I) complexes

and proposed mechanisms as compared with their computationally-modeled

counterparts. No aim is made to identify a “recommended” computational method for

investigations of gold catalysis; rather, discrepancies between experimentally and

computationally obtained values are highlighted, and the systematic errors between

different computational methods are discussed.

Second worldwide proficiency study on variable number of tandem repeats typing of Mycobacterium tuberculosis complex

Global Network for the Molecular Surveillance of Tuberculosis 2010: A. Miranda (Tuberculosis Laboratory of the National Institute of Health, Porto, Portugal)

Quantitative phase Analisis: A comparative study of Mo and Cu strictly monochromatic radiations

A comparison of the Rietveld quantitative phase analyses (RQPA) obtained using Cu-Kα1, Mo-Kα1, and synchrotron strictly monochromatic radiations is presented. The main aim is to test a simple hypothesis: high energy Mo-radiation, combined with high resolution laboratory X-ray powder diffraction optics, could yield more accurate RQPA, for challenging samples, than well-established Cu-radiation procedure(s). In order to do so, three set of mixtures with increasing amounts of a given phase (spiking-method) were prepared and the corresponding RQPA results have been evaluated. Firstly, a series of crystalline inorganic phase mixtures with increasing amounts of an analyte was studied in order to determine if Mo-Kα1 methodology is as robust as the well-established Cu-Kα1 one. Secondly, a series of crystalline organic phase mixtures with increasing amounts of an organic compound was analyzed. This type of mixture can result in transparency problems in reflection and inhomogeneous loading in narrow capillaries for transmission studies. Finally, a third series with variable amorphous content was studied. Limit of detection in Cu-patterns, ~0.2 wt%, are slightly lower than those derived from Mo-patterns, ~0.3 wt%, for similar recording times and limit of quantification for a well crystallized inorganic phase using laboratory powder diffraction was established ~0.10 wt%. However, the accuracy was comprised as relative errors were ~100%. Contents higher than 1.0 wt% yielded analyses with relative errors lower than 20%. From the obtained results it is inferred that RQPA from Mo-Kα1 radiation have slightly better accuracies than those obtained from Cu-Kα1. This behavior has been established with the calibration graphics obtained through the spiking method and also from Kullback-Leibler distance statistic studies. We explain this outcome, in spite of the lower diffraction power for Mo-radiation (compared to Cu-radiation), due to the larger volume tested with Mo, also because higher energy minimize pattern systematic errors and the microabsorption effect.

From the traditional verification approach to the spatial methods: a study of applicability of the SAL metric in the framework of the WMO project MesoVICT

Increasing in resolution of numerical weather prediction models has allowed more and more realistic forecasts of atmospheric parameters. Due to the growing variability into predicted fields the traditional verification methods are not always able to describe the model ability because they are based on a grid-point-by-grid-point matching between observation and prediction. Recently, new spatial verification methods have been developed with the aim of show the benefit associated to the high resolution forecast. Nested in among of the MesoVICT international project, the initially aim of this work is to compare the newly tecniques remarking advantages and disadvantages. First of all, the MesoVICT basic examples, represented by synthetic precipitation fields, have been examined. Giving an error evaluation in terms of structure, amplitude and localization of the precipitation fields, the SAL method has been studied more thoroughly respect to the others approaches with its implementation in the core cases of the project. The verification procedure has concerned precipitation fields over central Europe: comparisons between the forecasts performed by the 00z COSMO-2 model and the VERA (Vienna Enhanced Resolution Analysis) have been done. The study of these cases has shown some weaknesses of the methodology examined; in particular has been highlighted the presence of a correlation between the optimal domain size and the extention of the precipitation systems. In order to increase ability of SAL, a subdivision of the original domain in three subdomains has been done and the method has been applied again. Some limits have been found in cases in which at least one of the two domains does not show precipitation. The overall results for the subdomains have been summarized on scatter plots. With the aim to identify systematic errors of the model the variability of the three parameters has been studied for each subdomain.

Protein cutoff scanning: a comparative analysis of cutoff dependent and cutoff free methods for prospecting contacts in proteins.

In this study, we carried out a comparative analysis between two classical methodologies to prospect residue contacts in proteins: the traditional cutoff dependent (CD) approach and cutoff free Delaunay tessellation (DT). In addition, two alternative coarse-grained forms to represent residues were tested: using alpha carbon (CA) and side chain geometric center (GC). A database was built, comprising three top classes: all alpha, all beta, and alpha/beta. We found that the cutoff value? at about 7.0 A emerges as an important distance parameter.? Up to 7.0 A, CD and DT properties are unified, which implies that at this distance all contacts are complete and legitimate (not occluded). We also have shown that DT has an intrinsic missing edges problem when mapping the first layer of neighbors. In proteins, it may produce systematic errors affecting mainly the contact network in beta chains with CA. The almost-Delaunay (AD) approach has been proposed to solve this DT problem. We found that even AD may not be an advantageous solution. As a consequence, in the strict range up ? to 7.0 A, the CD approach revealed to be a simpler, more complete, and reliable technique than DT or AD. Finally, we have shown that coarse-grained residue representations may introduce bias in the analysis of neighbors in cutoffs up to ? 6.8 A, with CA favoring alpha proteins and GC favoring beta proteins. This provides an additional argument pointing to ? the value of 7.0 A as an important lower bound cutoff to be used in contact analysis of proteins.

Exploiting spectrally resolved satellite observations to assess the performance of climate models

The accurate representation of the Earth Radiation Budget by General Circulation Models (GCMs) is a fundamental requirement to provide reliable historical and future climate simulations. In this study, we found reasonable agreement between the integrated energy fluxes at the top of the atmosphere simulated by 34 state-of-the-art climate models and the observations provided by the Cloud and Earth Radiant Energy System (CERES) mission on a global scale, but large regional biases have been detected throughout the globe. Furthermore, we highlighted that a good agreement between simulated and observed integrated Outgoing Longwave Radiation (OLR) fluxes may be obtained from the cancellation of opposite-in-sign systematic errors, localized in different spectral ranges. To avoid this and to understand the causes of these biases, we compared the observed Earth emission spectra, measured by the Infrared Atmospheric Sounding Interferometer (IASI) in the period 2008-2016, with the synthetic radiances computed on the basis of the atmospheric fields provided by the EC-Earth GCM. To this purpose, the fast σ-IASI radiative transfer model was used, after its validation and implementation in EC-Earth. From the comparison between observed and simulated spectral radiances, a positive temperature bias in the stratosphere and a negative temperature bias in the middle troposphere, as well as a dry bias of the water vapor concentration in the upper troposphere, have been identified in the EC-Earth climate model. The analysis has been performed in clear-sky conditions, but the feasibility of its extension in the presence of clouds, whose impact on the radiation represents the greatest source of uncertainty in climate models, has also been proven. Finally, the analysis of simulated and observed OLR trends indicated good agreement and provided detailed information on the spectral fingerprints of the evolution of the main climate variables.

Systematic and random errors between collocated satellite ice water path observations

There remains large disagreement between ice-water path (IWP) in observational data sets, largely because the sensors observe different parts of the ice particle size distribution. A detailed comparison of retrieved IWP from satellite observations in the Tropics (!30 " latitude) in 2007 was made using collocated measurements. The radio detection and ranging(radar)/light detection and ranging (lidar) (DARDAR) IWP data set, based on combined radar/lidar measurements, is used as a reference because it provides arguably the best estimate of the total column IWP. For each data set, usable IWP dynamic ranges are inferred from this comparison. IWP retrievals based on solar reflectance measurements, in the moderate resolution imaging spectroradiometer (MODIS), advanced very high resolution radiometer–based Climate Monitoring Satellite Applications Facility (CMSAF), and Pathfinder Atmospheres-Extended (PATMOS-x) datasets, were found to be correlated with DARDAR over a large IWP range (~20–7000 g m -2 ). The random errors of the collocated data sets have a close to lognormal distribution, and the combined random error of MODIS and DARDAR is less than a factor of 2, which also sets the upper limit for MODIS alone. In the same way, the upper limit for the random error of all considered data sets is determined. Data sets based on passive microwave measurements, microwave surface and precipitation products system (MSPPS), microwave integrated retrieval system (MiRS), and collocated microwave only (CMO), are largely correlated with DARDAR for IWP values larger than approximately 700 g m -2 . The combined uncertainty between these data sets and DARDAR in this range is slightly less MODIS-DARDAR, but the systematic bias is nearly an order of magnitude.

Impact of random and systematic recall errors and selection bias in case--control studies on mobile phone use and brain tumors in adolescents (CEFALO study)

Whether the use of mobile phones is a risk factor for brain tumors in adolescents is currently being studied. Case--control studies investigating this possible relationship are prone to recall error and selection bias. We assessed the potential impact of random and systematic recall error and selection bias on odds ratios (ORs) by performing simulations based on real data from an ongoing case--control study of mobile phones and brain tumor risk in children and adolescents (CEFALO study). Simulations were conducted for two mobile phone exposure categories: regular and heavy use. Our choice of levels of recall error was guided by a validation study that compared objective network operator data with the self-reported amount of mobile phone use in CEFALO. In our validation study, cases overestimated their number of calls by 9% on average and controls by 34%. Cases also overestimated their duration of calls by 52% on average and controls by 163%. The participation rates in CEFALO were 83% for cases and 71% for controls. In a variety of scenarios, the combined impact of recall error and selection bias on the estimated ORs was complex. These simulations are useful for the interpretation of previous case-control studies on brain tumor and mobile phone use in adults as well as for the interpretation of future studies on adolescents.

Systematic diagonal and vertical errors in antisaccades and memory-guided saccades

Studies of memory-guided saccades in monkeys show an upward bias, while studies of antisaccades in humans show a diagonal effect, a deviation of endpoints toward the 45° diagonal. To determine if these two different spatial biases are specific to different types of saccades, we studied prosaccades, antisaccades and memory-guided saccades in humans. The diagonal effect occurred not with prosaccades but with antisaccades and memory-guided saccades with long intervals, consistent with hypotheses that it originates in computations of goal location under conditions of uncertainty. There was a small upward bias for memory-guided saccades but not prosaccades or antisaccades. Thus this bias is not a general effect of target uncertainty but a property specific to memory-guided saccades.

Errors in the administration of medication in inpatient hospitals: A systematic review of the research literature on commercial computerized physician order entry systems

Errors in the administration of medication represent a significant loss of medical resources and pose life altering or life threatening risks to patients. This paper considered the question, what impact do Computerized Physician Order Entry (CPOE) systems have on medication errors in the hospital inpatient environment? Previous reviews have examined evidence of the impact of CPOE on medication errors, but have come to ambiguous conclusions as to the impact of CPOE and decision support systems (DSS). Forty-three papers were identified. Thirty-one demonstrated a significant reduction in prescribing error rates for all or some drug types; decreases in minor errors were most often reported. Several studies reported increases in the rate of duplicate orders and failures to remove contraindicated drugs, often attributed to inappropriate design or to an inability to operate the system properly. The evidence on the effectiveness of CPOE to reduce errors in medication administration is compelling though it is limited by modest study sample sizes and designs. ^

Medication errors in mental healthcare:a systematic review

Methods: It has been estimated that medication error harms 1-2% of patients admitted to general hospitals. There has been no previous systematic review of the incidence, cause or type of medication error in mental healthcare services. Methods: A systematic literature search for studies that examined the incidence or cause of medication error in one or more stage(s) of the medication-management process in the setting of a community or hospital-based mental healthcare service was undertaken. The results in the context of the design of the study and the denominator used were examined. Results: All studies examined medication management processes, as opposed to outcomes. The reported rate of error was highest in studies that retrospectively examined drug charts, intermediate in those that relied on reporting by pharmacists to identify error and lowest in those that relied on organisational incident reporting systems. Only a few of the errors identified by the studies caused actual harm, mostly because they were detected and remedial action was taken before the patient received the drug. The focus of the research was on inpatients and prescriptions dispensed by mental health pharmacists. Conclusion: Research about medication error in mental healthcare is limited. In particular, very little is known about the incidence of error in non-hospital settings or about the harm caused by it. Evidence is available from other sources that a substantial number of adverse drug events are caused by psychotropic drugs. Some of these are preventable and might probably, therefore, be due to medication error. On the basis of this and features of the organisation of mental healthcare that might predispose to medication error, priorities for future research are suggested.

A systematic approach to error isolation in computerized wastewater simulation models

Activated sludge models are used extensively in the study of wastewater treatment processes. While various commercial implementations of these models are available, there are many people who need to code models themselves using the simulation packages available to them, Quality assurance of such models is difficult. While benchmarking problems have been developed and are available, the comparison of simulation data with that of commercial models leads only to the detection, not the isolation of errors. To identify the errors in the code is time-consuming. In this paper, we address the problem by developing a systematic and largely automated approach to the isolation of coding errors. There are three steps: firstly, possible errors are classified according to their place in the model structure and a feature matrix is established for each class of errors. Secondly, an observer is designed to generate residuals, such that each class of errors imposes a subspace, spanned by its feature matrix, on the residuals. Finally. localising the residuals in a subspace isolates coding errors. The algorithm proved capable of rapidly and reliably isolating a variety of single and simultaneous errors in a case study using the ASM 1 activated sludge model. In this paper a newly coded model was verified against a known implementation. The method is also applicable to simultaneous verification of any two independent implementations, hence is useful in commercial model development.

Systematic difference between blood pressure readings caused by cuff type.

In this study we determine whether blood pressure readings using a cuff of fixed size systematically differed from readings made with a triple-bladder cuff (Tricuff) that automatically adjusts bladder width to arm circumference and assessed subsequent clinical and epidemiological effects. Blood pressure was measured with a standard cuff or a Tricuff in 454 patients visiting an outpatient clinic in the Seychelles (Indian Ocean). Overall means of within-individual standard cuff-Tricuff differences in systolic and diastolic blood pressures were examined in relation to arm circumference and sex. The standard cuff-Tricuff difference in systolic and diastolic blood pressures increased monotonically with circumference (from 4.7 +/- 0.8/3.2 +/- 0.7 mm Hg for arm circumference of 30 to 31 cm to 10.0 +/- 1.1/8.0 +/- 0.9 mm Hg for arm circumference > or = 36 cm) and was larger in women than men. Multivariate linear regression indicated independent effects of arm circumference and sex. Forty percent of subjects with a diastolic blood pressure of > or = 95 mm Hg measured with a standard cuff had values less than 95 mm Hg measured with a Tricuff. Extrapolation to the entire population of the Seychelles decreased the prevalence of blood pressure greater than or equal to 160/95 mm Hg by 11.5% and 24.0% in men and women, respectively, aged 35 to 64 years. The age-adjusted effect of body mass index on systolic and diastolic blood pressures decreased twofold using blood pressure readings made with a Tricuff instead of a standard cuff.(ABSTRACT TRUNCATED AT 250 WORDS)

Novel Interaction Techniques for Mobile Augmented Reality applications. A Systematic Literature Review

This study reviews the research on interaction techniques and methods that could be applied in mobile augmented reality scenarios. The review is focused on themost recent advances and considers especially the use of head-mounted displays. Inthe review process, we have followed a systematic approach, which makes the reviewtransparent, repeatable, and less prone to human errors than if it was conducted in amore traditional manner. The main research subjects covered in the review are headorientation and gaze-tracking, gestures and body part-tracking, and multimodality– as far as the subjects are related to human-computer interaction. Besides these,also a number of other areas of interest will be discussed.

Efficient and cost-effective experimental determination of kinetic constants and data: the success of a Bayesian systematic approach to drug transport, receptor binding, continuous culture and cell transport kinetics

Details about the parameters of kinetic systems are crucial for progress in both medical and industrial research, including drug development, clinical diagnosis and biotechnology applications. Such details must be collected by a series of kinetic experiments and investigations. The correct design of the experiment is essential to collecting data suitable for analysis, modelling and deriving the correct information. We have developed a systematic and iterative Bayesian method and sets of rules for the design of enzyme kinetic experiments. Our method selects the optimum design to collect data suitable for accurate modelling and analysis and minimises the error in the parameters estimated. The rules select features of the design such as the substrate range and the number of measurements. We show here that this method can be directly applied to the study of other important kinetic systems, including drug transport, receptor binding, microbial culture and cell transport kinetics. It is possible to reduce the errors in the estimated parameters and, most importantly, increase the efficiency and cost-effectiveness by reducing the necessary amount of experiments and data points measured. (C) 2003 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.