Oxidation chemistry of d^0 organometallic complexes

Electron-transfer processes can play an important role in organometallic chemistry. Herein, we demonstrate that even d^0 organometallic complexes exhibit a rich redox chemistry and present electrochemical, kinetics, and stereochemical studies that establish a general outer-sphere oxidation process for d^0 group 4 metallocene complexes. This oxidation chemistry closely parallels the reported LMCT photochemistry of these complexes

Ternary Nitride Semiconductors in the Rocksalt Crystal Structure

Inorganic nitrides with wurtzite crystal structures are well-known semiconductors used in optoelectronic devices. In contrast, rocksalt-based nitrides are known for their metallic and refractory properties. Breaking this dichotomy, here we report on ternary nitride semiconductors with rocksalt crystal structures, remarkable optoelectronic properties, and the general chemical formula Mg$_{x}$TM$_{1-x}$N (TM=Ti, Zr, Hf, Nb). These compounds form over a broad metal composition range and our experiments show that Mg-rich compositions are nondegenerate semiconductors with visible-range optical absorption onsets (1.8-2.1 eV). Lattice parameters are compatible with growth on a variety of substrates, and epitaxially grown MgZrN$_{2}$ exhibits remarkable electron mobilities approaching 100 cm$^{2}$V$^{-1}$s$^{-1}$. Ab initio calculations reveal that these compounds have disorder-tunable optical properties, large dielectric constants and low carrier effective masses that are insensitive to disorder. Overall, these experimental and theoretical results highlight Mg$_{G-3}$TMN$_{G-2}$ rocksalts as a new class of semiconductor materials with promising properties for optoelectronic applications

Regional variations in diffuse nitrogen losses from agriculture in the Nordic and Baltic regions

International audienceThis paper describes nitrogen losses from, and the characteristics of, 35 selected catchments (12 to 2000 ha) in the Nordic and Baltic countries. Average annual losses of N in 1994?1997 ranged from 5 to 75 kg ha-1, generally highest and characterised by significant within-country and interannual variations, in Norway and the lowest losses were observed in the Baltic countries. An important finding of the study is that the average nutrient losses varied greatly among the studied catchments. The main explanations for this variability were water runoff, fertiliser use (especially the amount of manure), soil type and erosion (including stream bank erosion). However, there were several exceptions, and it was difficult to find general relationships between the individual factors. For example, there was poor correlation between nitrogen losses and surpluses. Therefore, the results suggest that the observed variability in N losses cannot have been due solely to differences in farm management practices, although the studied catchments do include a wide range of nutrient application levels, animal densities and other relevant elements. There is considerable spatial variation in the physical properties (soil, climate, hydrology, and topography) and the agricultural management of the basins, and the interaction between and relative effects of these factors has an important impact on erosion and nutrient losses. In particular, hydrological processes may have a marked effect on N losses measured in the catchment stream water. The results indicate that significant differences in hydrological pathways (e.g. the relationship between fast- and slow-flow processes) lead to major regional differences in N inputs to surface waters and therefore also in the response to changes in field management practices. Agricultural practices such as crop rotation systems, nutrient inputs and soil conservation measures obviously play a significant role in the site-specific effects, although they cannot explain the large regional differences observed in this study. The interactions between agricultural practices and basic catchment characteristics, including hydrological processes, determine the final losses of nitrogen to surface waters, hence it is necessary to understand these interactions to manage diffuse losses of agricultural nutrients efficiently. Keywords: agriculture, catchments, diffuse sources, nitrogen, losses, Baltic, Nordi

Oxidation chemistry of d^0 organometallic complexes

Electron-transfer processes can play an important role in organometallic chemistry. Herein, we demonstrate that even d^0 organometallic complexes exhibit a rich redox chemistry and present electrochemical, kinetics, and stereochemical studies that establish a general outer-sphere oxidation process for d^0 group 4 metallocene complexes. This oxidation chemistry closely parallels the reported LMCT photochemistry of these complexes

Validity of the Brazilian version of the freezing of gait questionnaire

Objective: To validate the freezing of gait questionnaire (FOG-Q) for a Brazilian population of Parkinson's disease (PD) patients. Methods: One hundred and seven patients with a diagnosis of PD were evaluated by shortened UPDRS motor scale (sUPDRm), Hoehn and Yahr (HY), Schwab and England scale (SE), Berg balance scale (BBS), falls efficacy scale international (FES-I), gait and balance scale (GABS), and the FOG-Q Brazilian version. Results: 47.7% of PD patients had FOG episodes; this group had worse scores on sUPDRSm, FOGQ, FES-I, BBS, GABS and FOG item of UPDRS when compared to the PD group without FOG. The internal consistency was 0.86, intra-rater 0.82 and inter-rater 0.78. The FOG-Q Brazilian version was significantly correlated with items related to gait and balance. The ROC curve was 0.94, the sensitivity was 0.90 and specificity was 0.92. Conclusion: Our study suggests that the FOG-Q Brazilian version is a reliable and valid instrument for assessing FOG in PD patients.Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES

Chemical conversions in supercritical media: Environmentally sound approaches to processes and materials

This is the final report of a two-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The aim of this effort was to evaluate the potential of supercritical fluids (SCF) as reaction media in an effort to develop new, environmentally-friendly methods for chemical synthesis or processing. The use of novel media creates the possibility of opening up substantially different chemical pathways, increasing selectivity (eliminating waste by-products), and enhancing reaction rates (decreasing hold-up times and saving energy). In addition, the use of SCF as reaction media facilitates downstream separations and mitigate or eliminate the need for hazardous solvents on scales from bench top to production. This project employed a highly interdisciplinary approach to investigate the utility of SCFs as reaction media for polymer synthesis and synthetic organic chemistry

The Prevalence and Correlation of Non-motor Symptoms in Adult Patients with Idiopathic Focal or Segmental Dystonia

Background: Idiopathic focal dystonia is a motor syndrome associated with dysfunction of basal ganglia circuits. Observations have suggested that many other non-motor symptoms may also be part of the clinical picture. The aim was to assess the prevalence and correlation of non-motor symptoms in patients with common idiopathic focal or segmental dystonia. Methods: In a single-center cross-sectional case–control study, we evaluated the presence of pain, neuropsychiatric symptoms, and sleep alterations in 28 patients with blepharospasm, 28 patients with cervical dystonia, 24 patients with writer’s cramp, and 80 control subjects matched for sex, age, and schooling. We obtained clinical and demographic data, and evaluated patients using the Fahn–Marsden Dystonia Rating Scale and other specific scales for dystonia. All subjects completed the following questionnaires: Beck Depression Inventory, Beck Anxiety Inventory, Social Phobia Inventory, Apathy Scale, Epworth Sleepiness Scale, Pittsburgh Sleep Quality Index, Brief Pain Scale, and the World Health Organization Quality of Life brief scale. Results: The patients presented more symptoms of depression, anxiety, and apathy than the control subjects. They also reported worse quality of sleep and more pain complaints. Patients with blepharospasm were the most symptomatic subgroup. The patients had worse quality of life, and the presence of pain and symptoms of apathy and depression were the main influences for these findings, but not the severity of motor symptoms. Discussion: Patients with dystonia, especially those with blepharospasm, showed higher prevalence of symptoms of depression, anxiety, apathy, worse quality of sleep, and pain. These symptoms had a negative impact on their quality of life