A Comparative Study of Electrochemical Reduction of 4‐Nitrophenyl Covalently Grafted on Gold and Carbon

4‐Nitrophenyl layers were grafted on gold and glassy carbon surfaces by electrochemical reductive adsorption of the corresponding diazonium salt. Electrochemical conversion efficiencies of 4‐nitrophenyl moieties to 4‐aminophenyl moieties on gold versus on glassy carbon in a protic medium were investigated using X‐ray photoelectron spectroscopy (XPS). In total contrast to all previous comparative studies showing greater electrochemical reactivity of aryl diazonium salt‐derived layers on gold than on glassy carbon, a much lower rate of conversion to 4‐aminophenyl was observed on gold than on glassy carbon by both cyclic voltammetry (CV) and chronoamperometry (CA) methods. The lower electron transfer rate during conversion observed on gold versus glassy carbon was proposed to be due to a mechanism related to the molecular structure rearrangement of 4‐nitrophenyl during the process on glassy carbon. However, whilst complete conversion of 4‐nitrophenyl to 4‐aminophenyl on gold by chronoamperometry was achieved, on glassy carbon complete reduction could not be achieved under the same conditions.     

Development of T2-relaxation values in regional brain sites during adolescence

Brain tissue changes accompany multiple neurodegenerative and developmental conditions in adolescents. Complex processes that occur in the developing brain with disease can be evaluated accurately only against normal aging processes. Normal developmental changes in different brain areas alter tissue water content, which can be assessed by magnetic resonance (MR) T2 relaxometry. We acquired proton-density (PD) and T2-weighted images from 31 subjects (mean age±S.D., 17.4±4.9 years; 18 male), using a 3.0-T MR imaging scanner. Voxel-by-voxel T2-relaxation values were calculated, and whole-brain T2-relaxation maps constructed and normalized to a common space template. We created a set of regions of interest (ROIs) over cortical gray and white matter, basal ganglia, amygdala, thalamic, hypothalamic, pontine and cerebellar sites, with sizes of ROIs varying from 12 to 243 mm³; regional T2-relaxation values were determined from these ROIs and normalized T2-relaxation maps. Correlations between R2 (1/T2) values in these sites and age were assessed with Pearson's correlation procedures, and gender differences in regional T2-relaxation values were evaluated with independent-samples t tests. Several brain regions, but not all, showed principally positive correlations between R2 values and age; negative correlations emerged in the cerebellar peduncles. No significant differences in T2-relaxation values emerged between males and females for those areas, except for the mid pons and left occipital white matter; males showed higher T2-relaxation values over females. The findings indicate that T2-relaxation values vary with development between brain structures, and emphasize the need to correct for such age-related effects during any determination of potential changes from control values.     

Evaluating the accuracy of theoretical one‐bond 13C─13C scalar couplings and their ability to predict structure in a natural product

This study explores the feasibility of using a combination of experimental and theoretical 1‐bond ¹³C─¹³C scalar couplings (¹J_CC) to establish structure in organic compounds, including unknowns. Historically, ⁿJ_CC and ⁿJ_CH studies have emphasized 2 and 3‐bond couplings, yet ¹J_CC couplings exhibit significantly larger variations. Moreover, recent improvements in experimental measurement and data processing methods have made ¹J_CC data more available. Herein, an approach is evaluated in which a collection of theoretical structures is created from a partial nuclear magnetic resonance structural characterization. Computed ¹J_CC values are compared to experimental data to identify candidates giving the best agreement. This process requires knowledge of the error in theoretical methods, thus the B3LYP, B3PW91, and PBE0 functionals are evaluated by comparing to 27 experimental values from INADEQUATE. Respective errors of ±1.2, ±3.8, and ±2.3 Hz are observed. An initial test of this methodology involves the natural product 5‐methylmellein. In this case, only a single candidate matches experimental data with high statistical confidence. This analysis establishes the intramolecular hydrogen‐bonding arrangement, ring heteroatom identity, and conformation at one position. This approach is then extended to hydroheptelidic acid, a natural product not fully characterized in prior studies. The experimental/theoretical approach proposed herein identifies a single best‐fit structure from among 26 candidates and establishes, for the first time, 1 configuration and 3 conformations to complete the characterization. These results suggest that accurate and complete structural characterizations of many moderately sized organic structures (<800 Da) may be possible using only ¹J_CC data.     

Direct olive oil analysis by low‐temperature plasma (LTP) ambient ionization mass spectrometry

A fast, reagentless, and direct method is presented for the mass spectrometric analysis of olive oil without any sample pretreatment whatsoever. An ambient ionization technique, the low‐temperature plasma (LTP) probe, based on dielectric barrier discharge, is used to detect both minor and trace components (free fatty acids, phenolics and volatiles) in raw untreated olive oil. The method allows the measurement of free fatty acids (the main quality control parameter used to grade olive oil according to quality classes), selected bioactive phenolic compounds, and volatiles. The advantages and limitations of the direct analysis of extremely complex mixtures by the ambient ionization/tandem mass spectrometry combination are discussed and illustrated. The data presage the possible large‐scale application of direct mass spectrometric analysis methods in the characterization of olive oil and other foodstuffs. Copyright © 2009 John Wiley & Sons, Ltd.     

Prospects for the search for a standard model Higgs boson in ATLAS using vector boson fusion

The European Physical Journal C - The potential for the discovery of a Standard Model Higgs boson in the mass range m H &lt; 2 m Z in the vector boson fusion mode has been studied for the ATLAS...     

Towards An Intelligent Maintenance Optimization System

This paper is concerned with the evaluation and enhancement of the maintenance routines of large and complex technical systems. An ‘intelligent decision support system’ approach is suggested as a method for overcoming the difficulties associated with the scale, variability and changeability of such systems. The main features of the proposed intelligent maintenance optimization system (IMOS) are identified. A prototype system is then presented and its main mathematical models of maintenance are introduced. Some sample test data and the results produced from them are presented. Other aspects discussed include dealing with censored data, optimization criteria, the development of a maintenance model selection rule base, the recognition of data patterns and models' robustness. Results of IMOS system validation against expert advice have shown a high measure of consistency.     

Laser Machined Plastic Laminates: Towards Portable Diagnostic Devices for Use in Low Resource Environments

Despite significant progress in development of bioanalytical devices cost, complexity, access to reagents and lack of infrastructure have prevented use of these technologies in resource‐limited regions. To provide a sustainable tool in the global effort to combat infectious diseases the diagnostic device must be low cost, simple to operate and read, robust, and have sensitivity and specificity comparable to laboratory analysis. In this mini‐review we describe recent work using laser machined plastic laminates to produce diagnostic devices that are capable of a wide variety of bioanalytical measurements and show great promise towards future use in low‐resource environments.     

Ionic liquid effects on Mizoroki-Heck reactions: more than just carbene complex formation

Reaction profiles for a Mizoroki-Heck reaction in either an ionic liquid or a molecular solvent with different palladium sources demonstrate that the rate enhancements observed in ionic liquids cannot be solely attributed to Pd-carbene complex formation.