Exploration of 1,2-phenylenediboronic esters as potential bidentate catalysts for organic synthesis

Recently, we described the first inverse electron demand Diels-Alder reaction of 1,2-diazene catalyzed by a bidentate Lewis acid. Herein we investigate 1,2-phenylenediboronic esters as potential catalysts for this transformation offering higher stability and easier handling than the currently used boranthracene derivatives. Different 1,2-phenylenediboronic esters were prepared and their ability to form bidentate coordination complexes with phthalazine was analyzed. Although a 1:1 complex was observed, X-ray analysis revealed binding only in a monodentate fashion. Graphical abstrac

Iron Ore Tailings Dewatering: Measurement of Adhesion and Cohesion for Filter Press Operation

Globally, mining operators focus increasingly on tailings filtration to recover process water and store tailings more safely. Generally, required water contents below 20-w% are reached by using filter presses. To maintain high efficiency, complete cake detachment is needed because incomplete discharge reduces plant performance. However, filter cake discharge can occur in different ways, mainly influenced by adhesion of the filter cake to the filter cloth as well as by cohesion of the cake. Therefore, this study points out different major detachment behaviors and a theoretical approach to describe them. Furthermore, investigations on iron ore tailings filtrations were carried out to show the influences of different filter media, different filtration pressure and cake post-treatment on adhesion and cohesion

Bidentate Lewis Acid Catalyzed Domino Diels-Alder Reaction of Phthalazine for the Synthesis of Bridged Oligocyclic Tetrahydronaphthalenes

A domino process consisting of an inverse and a normal electron-demand Diels-Alder reaction is presented for the formation of bridged tri- and tetracyclic 1,2,3,4-tetrahydronaphthalenes catalyzed by a bidentate Lewis acid. The products were synthesized in a one-pot reaction from commercially available starting materials and contain up to six stereogenic centers. The tetrahydronaphthalenes were isolated as single diastereomers and are derivatives of phenylethylamine, which is well-known as a scaffold of amphetamine or dopamine

Factor VIII: Long-established role in haemophilia A and emerging evidence beyond haemostasis

Abstract Factor VIII protein (FVIII) as a coagulation replacement factor has for decades been used as the standard of care for management of people with haemophilia A. It is effective for treatment of bleeding events, as prophylaxis to prevent bleeding events and preserve joint function, and to support surgery in people with haemophilia A. Despite long experience in treating haemophilia A, we are only beginning to understand the functions of FVIII beyond its established role as a coenzyme to factor IXa to expedite thrombin generation through the intrinsic pathway of coagulation. Here, we review the current role of FVIII coagulant (FVIII:C) in haemophilia A management and emerging evidence for the role of FVIII across multiple systems, including the cardiovascular system, angiogenesis and maintenance of bone health. For instance, supraphysiological FVIII levels are a risk factor for venous thromboembolism. von Willebrand factor (VWF), which forms a non-covalent complex with circulating FVIII, is an established marker and regulator of angiogenesis. In a mouse model of haemophilia, treatment with FVIII decreased expression of receptor activator of nuclear factor kappa-Β ligand (RANKL), a marker for bone turnover. Longitudinal follow-up data in people with haemophilia A are needed to confirm and extend these observations

ISO LWS Spectroscopy of M82: A Unified Evolutionary Model

We present the first complete far-infrared spectrum (43 to 197 um) of M82, the brightest infrared galaxy in the sky, taken with the Long Wavelength Spectrometer of the Infrared Space Observatory (ISO). We detected seven fine structure emission lines, [OI] 63 and 145 um, [OIII] 52 and 88 um, [NII] 122 um, [NIII] 57 um and [CII] 158 um, and fit their ratios to a combination starburst and photo-dissociation region (PDR) model. The best fit is obtained with HII regions with n = 250 cm^{-3} and an ionization parameter of 10^{-3.5} and PDRs with n = 10^{3.3} cm^{-3} and a far-ultraviolet flux of G_o = 10^{2.8}. We applied both continuous and instantaneous starburst models, with our best fit being a 3-5 Myr old instantaneous burst model with a 100 M_o cut-off. We also detected the ground state rotational line of OH in absorption at 119.4 um. No excited level OH transitions are apparent, indicating that the OH is almost entirely in its ground state with a column density ~ 4x10^{14} cm^{-2}. The spectral energy distribution over the LWS wavelength range is well fit with a 48 K dust temperature and an optical depth, tau_{Dust} proportional to lambda^{-1}.Comment: 23 pages, 4 figures, accepted by ApJ, Feb. 1, 199

Variability of the transitional T Tauri star T Chamaeleontis

We characterize the physical properties of T Chamaeleontis, a transitional T Tauri star showing UX Ori-type variability, and of its associated disc, and probe possible effects of disc clearing processes. Different spectral diagnostics are examined, based on a rich collection of optical high- and low-resolution spectra. We determine radial and projected rotational velocities, and measure equivalent widths of the Li I (6708 A) line and of the most prominent emission lines (e.g. Ha, Hb and [OI] 6300A); we analyse shape changes of photospheric lines via bisector-method, while variability in Ha and Hb is inspected through line-profile correlation matrices. The strength of the Ha and Hb emission is highly variable and well correlated with that of the [OI] lines, as well as with Av variations of over three magnitudes. Variations up to nearly 10 km/s in the radial velocity of the star are measured on analogous time-scale, but with no apparent periodicity. SED modelling confirms the existence of a gap in the disc. Variable circumstellar extinction is pointed out as responsible for the conspicuous variations observed in the stellar continuum flux and for concomitant changes in the emission features by contrast effect. Clumpy structures, incorporating large dust grains and orbiting the star within a few tenths of AU, obscure episodically the star and, eventually, part of the inner circumstellar zone, while the bulk of the hydrogen lines emitting zone and outer low-density wind region traced by the [OI] remain unaffected. Coherently with this scenario, the detected radial velocity changes are also explainable in terms of clumpy materials transiting and partially obscuring the star.Comment: 38 pages, 32 figures. To appear in the Astronomy and Astrophysics main journa

Spin-dependent transport in metal/semiconductor tunnel junctions

This paper describes a model as well as experiments on spin-polarized tunnelling with the aid of optical spin orientation. This involves tunnel junctions between a magnetic material and gallium arsenide (GaAs), where the latter is optically excited with circularly polarized light in order to generate spin-polarized carriers. A transport model is presented that takes account of carrier capture in the semiconductor surface states, and describes the semiconductor surface in terms of a spin-dependent energy distribution function. The so-called surface spin-splitting can be calculated from the balance of the polarized electron and hole flow in the semiconductor subsurface region, the polarized tunnelling current across the tunnel barrier between the magnetic material and the semiconductor surface, and the spin relaxation at the semiconductor surface. Measurements are presented of the circular-polarization-dependent photocurrent (the so-called helicity asymmetry) in thin-film tunnel junctions of Co/Al2O3/GaAs. In the absence of a tunnel barrier, the helicity asymmetry is caused by magneto-optical effects (magnetic circular dichroism). In the case where a tunnel barrier is present, the data cannot be explained by magneto-optical effects alone; the deviations provide evidence that spin-polarized tunnelling due to optical spin orientation occurs. In Co/τ-MnAl/AlAs/GaAs junctions no deviations from the magneto-optical effects are observed, most probably due to the weak spin polarization of τ-MnAl along the tunnelling direction; the latter is corroborated by bandstructure calculations. Finally, the application of photoexcited GaAs for spin-polarized tunnelling in a scanning tunnelling microscope is discussed.

Stable Isotope Metabolic Labeling with a Novel 15N-Enriched Bacteria Diet for Improved Proteomic Analyses of Mouse Models for Psychopathologies

The identification of differentially regulated proteins in animal models of psychiatric diseases is essential for a comprehensive analysis of associated psychopathological processes. Mass spectrometry is the most relevant method for analyzing differences in protein expression of tissue and body fluid proteomes. However, standardization of sample handling and sample-to-sample variability are problematic. Stable isotope metabolic labeling of a proteome represents the gold standard for quantitative mass spectrometry analysis. The simultaneous processing of a mixture of labeled and unlabeled samples allows a sensitive and accurate comparative analysis between the respective proteomes. Here, we describe a cost-effective feeding protocol based on a newly developed 15N bacteria diet based on Ralstonia eutropha protein, which was applied to a mouse model for trait anxiety. Tissue from 15N-labeled vs. 14N-unlabeled mice was examined by mass spectrometry and differences in the expression of glyoxalase-1 (GLO1) and histidine triad nucleotide binding protein 2 (Hint2) proteins were correlated with the animals' psychopathological behaviors for methodological validation and proof of concept, respectively. Additionally, phenotyping unraveled an antidepressant-like effect of the incorporation of the stable isotope 15N into the proteome of highly anxious mice. This novel phenomenon is of considerable relevance to the metabolic labeling method and could provide an opportunity for the discovery of candidate proteins involved in depression-like behavior. The newly developed 15N bacteria diet provides researchers a novel tool to discover disease-relevant protein expression differences in mouse models using quantitative mass spectrometry

Acute Cerebrovascular Disease in the Young The Stroke in Young Fabry Patients Study

Background and Purpose-Strokes have especially devastating implications if they occur early in life; however, only limited information exists on the characteristics of acute cerebrovascular disease in young adults. Although risk factors and manifestation of atherosclerosis are commonly associated with stroke in the elderly, recent data suggests different causes for stroke in the young. We initiated the prospective, multinational European study Stroke in Young Fabry Patients (sifap) to characterize a cohort of young stroke patients. Methods-Overall, 5023 patients aged 18 to 55 years with the diagnosis of ischemic stroke (3396), hemorrhagic stroke (271), transient ischemic attack (1071) were enrolled in 15 European countries and 47 centers between April 2007 and January 2010 undergoing a detailed, standardized, clinical, laboratory, and radiological protocol. Results-Median age in the overall cohort was 46 years. Definite Fabry disease was diagnosed in 0.5% (95% confidence interval, 0.4%-0.8%; n=27) of all patients; and probable Fabry disease in additional 18 patients. Males dominated the study population (2962/59%) whereas females outnumbered men (65.3%) among the youngest patients (18-24 years). About 80.5% of the patients had a first stroke. Silent infarcts on magnetic resonance imaging were seen in 20% of patients with a first-ever stroke, and in 11.4% of patients with transient ischemic attack and no history of a previous cerebrovascular event. The most common causes of ischemic stroke were large artery atherosclerosis (18.6%) and dissection (9.9%). Conclusions-Definite Fabry disease occurs in 0.5% and probable Fabry disease in further 0.4% of young stroke patients. Silent infarcts, white matter intensities, and classical risk factors were highly prevalent, emphasizing the need for new early preventive strategies

Spin Structure of the Proton from Polarized Inclusive Deep-Inelastic Muon-Proton Scattering

We have measured the spin-dependent structure function $g_1^p$ in inclusive deep-inelastic scattering of polarized muons off polarized protons, in the kinematic range $0.003 < x < 0.7$ and $1 GeV^2 < Q^2 < 60 GeV^2$. A next-to-leading order QCD analysis is used to evolve the measured $g_1^p(x,Q^2)$ to a fixed $Q^2_0$. The first moment of $g_1^p$ at $Q^2_0 = 10 GeV^2$ is $\Gamma^p = 0.136\pm 0.013(stat.) \pm 0.009(syst.)\pm 0.005(evol.)$. This result is below the prediction of the Ellis-Jaffe sum rule by more than two standard deviations. The singlet axial charge $a_0$ is found to be $0.28 \pm 0.16$. In the Adler-Bardeen factorization scheme, $\Delta g \simeq 2$ is required to bring $\Delta \Sigma$ in agreement with the Quark-Parton Model. A combined analysis of all available proton and deuteron data confirms the Bjorken sum rule.Comment: 33 pages, 22 figures, uses ReVTex and smc.sty. submitted to Physical Review