A modular flow reactor for performing Curtius rearrangements as a continuous flow process

The use of a mesofluidic flow reactor is described for performing Curtius rearrangement reactions of carboxylic acids in the presence of diphenylphosphoryl azide and trapping of the intermediate isocyanates with various nucleophiles.

Azide monoliths as convenient flow reactors for efficient Curtius rearrangement reactions

The preparation and use of an azide-containing monolithic reactor is described for use in a flow chemistry device and in particular for conducting Curtius rearrangement reactions via acid chloride inputs.

A bifurcated pathway to thiazoles and imidazoles using a modular flow microreactor

A scalable method for the preparation of 4,5-disubstituted thiazoles and imidazoles as distinct regioisomeric products using a modular flow microreactor has been devised. The process makes use of microfluidic reaction chips and packed immobilized-reagent columns to effect bifurcation of the reaction pathway.

A flow reactor process for the synthesis of peptides utilizing immobilized reagents, scavengers and catch and release protocols

A general flow process for the multi-step assembly of peptides has been developed and this procedure has been used to successfully construct a series of Boc, Cbz and Fmoc N-protected dipeptides in excellent yields and purities, including an extension of the method to enable the preparation of a tripeptide derivative.

Impact of non-hydrostatic effects and trapped lee waves on mountain wave drag in directionally sheared flow

The orographic gravity wave drag produced in flow over an axisymmetric mountain when both vertical wind shear and non-hydrostatic effects are important was calculated using a semi-analytical two-layer linear model, including unidirectional or directional constant wind shear in a layer near the surface, above which the wind is constant. The drag behaviour is determined by partial wave reflection at the shear discontinuity, wave absorption at critical levels (both of which exist in hydrostatic flow), and total wave reflection at levels where the waves become evanescent (an intrinsically non-hydrostatic effect), which produces resonant trapped lee wave modes. As a result of constructive or destructive wave interference, the drag oscillates with the thickness of the constant-shear layer and the Richardson number within it (Ri), generally decreasing at low Ri and when the flow is strongly non-hydrostatic. Critical level absorption, which increases with the angle spanned by the wind velocity in the constant-shear layer, shields the surface from reflected waves, keeping the drag closer to its hydrostatic limit. While, for the parameter range considered here, the drag seldom exceeds this limit, a substantial drag fraction may be produced by trapped lee waves, particularly when the flow is strongly non-hydrostatic, the lower layer is thick and Ri is relatively high. In directionally sheared flows with Ri = O(1), the drag may be misaligned with the surface wind in a direction opposite to the shear, a behaviour which is totally due to non-trapped waves. The trapped lee wave drag, whose reaction force on the atmosphere is felt at low levels, may therefore have a distinctly different direction from the drag associated with vertically propagating waves, which acts on the atmosphere at higher levels.

Detection of solar dimming and brightening effects on Northern Hemisphere river flow

Anthropogenic aerosols in the atmosphere have the potential to affect regional-scale land hydrology through solar dimming. Increased aerosol loading may have reduced historical surface evaporation over some locations, but the magnitude and extent of this effect is uncertain. Any reduction in evaporation due to historical solar dimming may have resulted in an increase in river flow. Here we formally detect and quantify the historical effect of changing aerosol concentrations, via solar radiation, on observed river flow over the heavily industrialized, northern extra-tropics. We use a state-of-the-art estimate of twentieth century surface meteorology as input data for a detailed land surface model, and show that the simulations capture the observed strong inter-annual variability in runoff in response to climatic fluctuations. Using statistical techniques, we identify a detectable aerosol signal in the observed river flow both over the combined region, and over individual river basins in Europe and North America. We estimate that solar dimming due to rising aerosol concentrations in the atmosphere around 1980 led to an increase in river runoff by up to 25% in the most heavily polluted regions in Europe. We propose that, conversely, these regions may experience reduced freshwater availability in the future, as air quality improvements are set to lower aerosol loading and solar dimming.

Flow-aligned jets in the magnetospheric cusp: Results from the Geospace Environment Modeling Pilot Program

The extended flight of the Airborne Ionospheric Observatory during the Geospace Environment Modeling (GEM) Pilot program on January 16, 1990, allowed continuous all-sky monitoring of the two-dimensional ionospheric footprint of the northward interplanetary magnetic field (IMF) cusp in several wavelengths. Especially important in determining the locus of magnetosheath electron precipitation was the 630.0-nm red line emission. The most striking morphological change in the images was the transient appearance of zonally elongated regions of enhanced 630.0-nm emission which resembled “rays” emanating from the centroid of the precipitation. The appearance of these rays was strongly correlated with the Y component of the IMF: when the magnitude of By was large compared to Bz, the rays appeared; otherwise, the distribution was relatively unstructured. Late in the flight the field of view of the imager included the field of view of flow measurements from the European incoherent scatter radar (EISCAT). The rays visible in 630.0-nm emission exactly aligned with the position of strong flow jets observed by EISCAT. We attribute this correspondence to the requirement of quasi-neutrality; namely, the soft electrons have their largest precipitating fluxes where the bulk of the ions precipitate. The ions, in regions of strong convective flow, are spread out farther along the flow path than in regions of weaker flow. The occurrence and direction of these flow bursts are controlled by the IMF in a manner consistent with newly opened flux tubes; i.e., when |By| > |Bz|, tension in the reconnected field lines produce east-west flow regions downstream of the ionospheric projection of the x line. We interpret the optical rays (flow bursts), which typically last between 5 and 15 min, as evidence of periods of enhanced dayside (or lobe) reconnection when |By| > |Bz|. The length of the reconnection pulse is difficult to determine, however, since strong zonal flows would be expected to persist until the tension force in the field line has decayed, even if the duration of the enhanced reconnection was relatively short.

Vertical ion flow in the polar ionosphere

Outflowing ions from the polar ionosphere fall into two categories: the classical polar wind and the suprathermal ion flows. The flows in both these categories vary a great deal with altitude. The classical polar wind is supersonic at high altitude: at ∼3 RE geocentric, the observed polar wind is H+ dominated and has a Mach number of 2.5–5.1. At 400–600 km, thermal and suprathermal upward O+ ion fluxes frequently occur at the poleward edge of the nightside auroral oval during magnetically active times. Above 500 km, ions are accelerated transverse to the local geomagnetic field. At 1400 km, transversely accelerated ions are frequently observed in winter nights but rarely appear in the summer. In the dayside cleft above ∼2000 km, ions of all species are transversely heated and upwell with significant number and heat fluxes, forming a cleft ion fountain as they convect across the polar cap. Upwelling ions are observed most (least) frequently in the summer (winter). At yet higher altitudes, energetic (>10 eV to several kiloelectron volts) upflowing H+ and O+ ions are frequently observed, their active time occurrence frequency being as high as 0.7 at auroral latitudes and 0.3 in the polar cap. Their composition, intensity, and angular characteristics vary quantitatively with solar activity, being O+ dominant and more intense near solar maximum. Their resulting ion outflow is dominated by ions below 1 keV and reaches 3.5×10^26 O+ and 7×10^25 H+ ions s^{−1} at magnetically active times (Kp≥5) near solar maximum. In comparison, the estimated polar wind ion outflow at times of moderate solar activity is 7×10^25H+ and 4×10^24 He+ ions s^{−1}. The estimated <10-eV cleft ion fountain flow is 3.8×10^25 O+ and 8.6×10^23 H+ ions s^{−1} near solar maximum.

Innovative approaches For enhancing the flow of funds into the Benefit Sharing Fund of the International Treaty on Plant Genetic Resources for Food and Agriculture: an evaluation of options

This report assesses the implications and revenue-generating potential of options for reform of the International Treaty on Plant Genetic Resources for Food and Agriculture in the context of the structure of the global seed industry and the emerging landscape of plant variety innovation for different crops. The implementation of these options would require modifications of Treaty and provisions of the Standard Material Transfer Agreements to alter the nature of payment obligations related to different categories of products, the payment rates under different options and the coverage of crops in Annex-I to the Treaty.

Kinetics analysis and automated online screening of aminocarbonylation of aryl halides in flow

Temperature, pressure, gas stoichiometry, and residence time were varied to control the yield and product distribution of the palladium-catalyzed aminocarbonylation of aromatic bromides in both a silicon microreactor and a packed-bed tubular reactor. Automation of the system set points and product sampling enabled facile and repeatable reaction analysis with minimal operator supervision. It was observed that the reaction was divided into two temperature regimes. An automated system was used to screen steady-state conditions for offline analysis by gas chromatography to fit a reaction rate model. Additionally, a transient temperature ramp method utilizing online infrared analysis was used, leading to more rapid determination of the reaction activation energy of the lower temperature regimes. The entire reaction spanning both regimes was modeled in good agreement with the experimental data.

Analysis of the genetic diversity and structure across a wide range of germplasm reveals prominent gene flow in apple at the European level

Abstract Background: The amount and structure of genetic diversity in dessert apple germplasm conserved at a European level is mostly unknown, since all diversity studies conducted in Europe until now have been performed on regional or national collections. Here, we applied a common set of 16 SSR markers to genotype more than 2,400 accessions across 14 collections representing three broad European geographic regions (North+East, West and South) with the aim to analyze the extent, distribution and structure of variation in the apple genetic resources in Europe. Results: A Bayesian model-based clustering approach showed that diversity was organized in three groups, although these were only moderately differentiated (FST=0.031). A nested Bayesian clustering approach allowed identification of subgroups which revealed internal patterns of substructure within the groups, allowing a finer delineation of the variation into eight subgroups (FST=0.044). The first level of stratification revealed an asymmetric division of the germplasm among the three groups, and a clear association was found with the geographical regions of origin of the cultivars. The substructure revealed clear partitioning of genetic groups among countries, but also interesting associations between subgroups and breeding purposes of recent cultivars or particular usage such as cider production. Additional parentage analyses allowed us to identify both putative parents of more than 40 old and/or local cultivars giving interesting insights in the pedigree of some emblematic cultivars. Conclusions: The variation found at group and sub-group levels may reflect a combination of historical processes of migration/selection and adaptive factors to diverse agricultural environments that, together with genetic drift, have resulted in extensive genetic variation but limited population structure. The European dessert apple germplasm represents an important source of genetic diversity with a strong historical and patrimonial value. The present work thus constitutes a decisive step in the field of conservation genetics. Moreover, the obtained data can be used for defining a European apple core collection useful for further identification of genomic regions associated with commercially important horticultural traits in apple through genome-wide association studies.

Peak expiratory flow values are higher in older and taller healthy male children: An observational study

Purpose: Peak expiratory flow (PEF) was measured in healthy children aged five to ten years in order to provide baseline values and to determine correlations between PEF and factors such as gender, age and type of school. Methods: After the Ethical Committee of Research in Human of the School of Medicine of ABC - FMABC approval, PEF and height were measured in 1942 children between five and ten years old from nine public schools and nine private schools throughout Sao Bernardo do Campo City. PEF was measured using the Mini-Wright Peak Flow Meter (Clement Clarke International Ltd.) and. height was measured using a Sanny professional stadiometer. Results: Significant differences were found in values for PEF: higher values were seen in older students in comparison with younger students, in males in comparison with females and in students from private schools in comparison with public schools, with average values ranging from 206 L/min to 248 L/min,. Linear correlations were seen for PEF values with both height and age (Spearman Coefficient). Conclusions: Differences were seen for PEF between genders and between types of school, and a linear correlation was seen for PEF with both age and height in healthy children from five to ten years old.

DC traction load flow including AC distribution network

In the first part some information and characterisation about an AC distribution network that feeds traction substations and their possible influences on the DC traction load flow are presented. Those influences are investigated and mathematically modelled. To corroborate the mathematical model, an example is presented and their results are confronted with real measurements.

Reduced gradient method combined with augmented Lagrangian and barrier for the optimal power flow problem

A new approach for solving the optimal power flow (OPF) problem is established by combining the reduced gradient method and the augmented Lagrangian method with barriers and exploring specific characteristics of the relations between the variables of the OPF problem. Computer simulations on IEEE 14-bus and IEEE 30-bus test systems illustrate the method. (c) 2007 Elsevier Inc. All rights reserved.

An evaluation of three upwinding approximations for numerical modeling the flow in tubular membrane of Newtonian and non-Newtonian fluids

In this paper, the laminar fluid flow of Newtonian and non-Newtonian of aqueous solutions in a tubular membrane is numerically studied. The mathematical formulation, with associated initial and boundary conditions for cylindrical coordinates, comprises the mass conservation, momentum conservation and mass transfer equations. These equations are discretized by using the finite-difference technique on a staggered grid system. Comparisons of the three upwinding schemes for discretization of the non-linear (convective) terms are presented. The effects of several physical parameters on the concentration profile are investigated. The numerical results compare favorably with experimental data and the analytical solutions. (C) 2011 Elsevier Inc. All rights reserved.