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The rational design and construction of a novel trinuclear macrocycle based on half-sandwich ruthenium was herein elaborated in detail, and consequently, fully characterized by 1D NMR, IR, EA and single crystal X-ray analysis, revealing its specific molecular structure which was a classic three-member ruthenium ring bridged by an organic linker [(E)-2-(2-(pyridin-4-yl)vinyl)quinolin-8-ol (HL)]. To further examine its photo and electronic properties, the mothed of UV–Vis and CV was carried out at ambient temperature, revealing it has a good application for catalyzing water oxidation under alkaline conditions.
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The von Willebrand factor (VWF) is a glycoprotein in the blood that plays a central role in hemostasis. Among other functions, VWF is responsible for platelet adhesion at sites of injury via its A1 domain. Its adjacent VWF domain A2 exposes a cleavage site under shear to degrade long VWF fibers in order to prevent thrombosis. Recently, it has been shown that VWF A1/A2 interactions inhibit the binding of platelets to VWF domain A1 in a force-dependent manner prior to A2 cleavage. However, whether and how this interaction also takes place in longer VWF fragments as well as the strength of this interaction in the light of typical elongation forces imposed by the shear flow of blood remained elusive. Here, we addressed these questions by using single molecule force spectroscopy (SMFS), Brownian dynamics (BD), and molecular dynamics (MD) simulations. Our SMFS measurements demonstrate that the A2 domain has the ability to bind not only to single A1 domains but also to VWF A1A2 fragments. SMFS experiments of a mutant [A2] domain, containing a disulfide bond which stabilizes the domain against unfolding, enhanced A1 binding. This observation suggests that the mutant adopts a more stable conformation for binding to A1. We found intermolecular A1/A2 interactions to be preferred over intramolecular A1/A2 interactions. Our data are also consistent with the existence of two cooperatively acting binding sites for A2 in the A1 domain. Our SMFS measurements revealed a slip-bond behavior for the A1/A2 interaction and their lifetimes were estimated for forces acting on VWF multimers at physiological shear rates using BD simulations. Complementary fitting of AFM rupture forces in the MD simulation range adequately reproduced the force response of the A1/A2 complex spanning a wide range of loading rates. In conclusion, we here characterized the auto-inhibitory mechanism of the intramolecular A1/A2 bond as a shear dependent safeguard of VWF, which prevents the interaction of VWF with platelets.
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Non-selective and subunit (GluN2B)-specific N-methyl-d-aspartate receptor (NMDAR) antagonists represent promising alternative antidepressant drugs with fast onset of the therapeutic action. The neuronal activation pattern induced by NMDAR antagonists is well characterized by c-Fos expression analysis only in the adult rodent brain. In contrast, there is little information available regarding their effects during postnatal development. Here we performed a systematic c-Fos brain mapping of the non-selective NMDAR antagonist MK-801 and the GluN2B-specific antagonist Ro 25-6981 from postnatal day 16 (P16) to P40. We found significant regional differences with gender-specificity in the activation pattern compared to the adult. Surprisingly, in the hippocampus, MK-801 triggered at pre-pubertal stages (especially at P24) very strong c-Fos expression, followed by low levels after P30, the approximate time point of puberty onset in mice. The cortical distribution of MK-801-triggered c-Fos expression before puberty differed also substantially from the adult brain, showing high levels only in deep cortical layers at pre-pubertal stages. In comparison, the cortical activation induced by Ro 25-6981 diminished from high pre-pubertal levels and was in comparison with that triggered by MK-801 low in the hippocampus. These results reveal highly dynamic changes in the c-Fos activation pattern induced by NMDAR antagonists during puberty.
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Valent-averaged diruthenium(II,III) tetraacetate, [Ru2(μ-O2CCH3)4(H2O)2](PF6), was reacted with various bidentate P–N donor ligands. These reactions led to the partial displacement of bridging carboxylate groups and concomitant cleavage of the Ru–Ru bond, producing novel complexes. Disassembly reactions with the aminophosphines; diphenyl-2-pyridylphosphine (dpppy) and 2-(diphenylphosphino)ethylamine (dppea), produced homoleptic tris-chelated species, fac-[Ru(dpppy-P,N)3](PF6)2 (III) and mer-[Ru(dppea-P,N)3](PF6)2 (VI), respectively. Disassembly reactions with aromatic aminophosphines; 2-(diphenylphosphino)methylpyridine (dppmpy) and 2-(diphenylphosphino)ethylpyridine (dppepy), led to heteroleptic tris-chelated complexes cis,cis,trans-[Ru(dppmpy-P,N)2(η2-O2CCH3)](PF6)·MeOH (IV) and cis,cis,trans-[Ru(dppepy-P,N)2(η2-O2CCH3)](PF6) (V), respectively, whereas reaction with the non-cyclic aminophosphine, 3-(diphenylphosphino)-1-propylamine (dpppa) and the non-cyclic iminophosphine, 2-(diphenylphosphino)benzylidinebenzylamine (dppbba), led to the heteroleptic tris-chelated complexes cis,cis,trans-[Ru(dpppa-P,N)2(η2-O2CCH3)](PF6·EtOH (VII) and cis,cis,trans-[Ru(dppbba-P,N)2(η2-O2CCH3)](PF6)·2MeOH·H2O (VIII), respectively. All complexes were fully characterized. Electrochemical studies (CV, OSWV) showed that the homoleptic tris-chelated complexes had higher oxidation potentials (Epa) than the corresponding heteroleptic tris-chelated complexes, due to the weak π-acceptor ability of the acetate group. Complex (III) has the highest Epa as it contains the strongest combination of π-accepting groups. The Epa values of the heteroleptic complexes were found to be in the order: dppbba (CHN)>dppmpy, dppepy (py)>dpppa (NH2), since amines are much poorer π-acceptors than pyridyl and imino groups. Complexes (III), (VI) and (VII) showed irreversible oxidation waves, while complexes (IV), (V) and (VIII) displayed quasi-reversible one electron processes.
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Active orthosis is one of the main research topics in the field of motor recovery. This paper deals with the design and control of an active knee orthosis driven by a customized rotary Series Elastic Actuator (SEA). The proposed actuator includes a DC motor, a worm gear and a customized torsion spring. Since the elastic element is the most important component in SEA design, a finite element analysis of the spring is performed to meet the specific requirements for knee assistance. Torque and impedance control are implemented to ensure secure interaction with the patient and to enable new strategies for rehabilitation. The torque controller, cascaded with an inner motor velocity control loop, is based on H∞ criterion to achieve good system performance with relation to parametric uncertainties and external disturbances. The impedance control is implemented using a PD position controller in cascade with the torque controller, where the outer position controller determines the desired torque according to position and velocity errors and impedance parameters. A variable impedance control strategy is then implemented to show the possibility to regulate the impedance of the knee joint during walking. Experiments considering the interaction between the subject and the active orthosis are performed to evaluate the proposed controllers.
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The objective of this study was to assess the prevalence of restless legs syndrome (RLS) among patients with stroke and to examine the anatomical correlation between location of stroke and RLS symptoms.
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A series of ruthenium(II) arene complexes (arene=p-cymene, hexamethylbenzene and benzene) containing dibenzoylmethane ligand (DBMH) of formula [(arene)Ru(DBM)Cl] and their ionic derivatives bearing PTA (1,3,5-triaza-7-phosphaadamantane), of formula [(arene)Ru(DBM)(PTA)]X (X=PF6- or SO3CF3-) have been synthesized and fully characterized. The solid-state structures of five complexes have been determined by single-crystal X-ray diffraction. These ruthenium materials exhibit intense photoluminescence emission at room temperature in the solid state. All complexes effectively bind to calf thymus DNA through intercalative/electrostatic interactions with more affinity for DNA minor groove. Finally, the antitumor activity of both ligand and complexes was evaluated against the U266 and RPMI human multiple myeloma cell lines, and some of them showed a cytotoxic and pro-apoptotic effect toward both cell lines.
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Voluminous Early Cretaceous volcanic rocks from the northern and central Lhasa subterranes contain important information on the tectono-magmatic processes. In this contribution, we focus on the Lower Cretaceous volcanic rocks in the Nagqu area, northern Lhasa subterrane, and present their zircon LA-ICP-MS U–Pb ages, in situ Hf isotopic data, whole-rock major and trace element compositions, and Sr–Nd isotopic data. The Nagqu volcanic rocks are high-K calc-alkaline to shoshonitic (K2O: 1.41–8.52wt.%; K2O/Na2O: 0.36–6.65) and feature similar geochemical characteristics (e.g., subparallel distribution of incompatible elements and REEs). Assimilation–fractional crystallization of magmas from identical source (rather than diverse magma sources) was mainly responsible for the formation of the diverse volcanic rock types. High Hf/Sm (>0.7) and high U/Yb whole-rock values and low Y values in zircon grains suggest the involvement of terrigenous components rather than subducted oceanic crust in the magma source. Tectonic discrimination diagrams, sedimentary environment (marine–continental transition), magma compositions (K-rich and terrigenous components), crustal thickening, and spatio-temporal variations in subduction, syn-collisional and post-collisional processes, indicate that the geodynamic setting of the Early Cretaceous magmatism was associated with the collision between the Lhasa and Qiangtang terranes. The high-K characteristics were inherited from the melts derived from the partial melting of lower metasomatized lithospheric mantle (the K-rich layer), which was transported to great depths by the continuously thickening lithosphere, eventually triggering melting.
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Reactions of [NH4]2[PdCl4] with N-protonated or N-alkyl-1,3,5-triaza-7-phosphaadamantane iodide salts [PTA-R]I (R=H, Me, Et, nPr, nBu) give the water-soluble palladium(II) complexes of type [PdI3(PTA-R)] in isolated yields of 62–81%. All these compounds have been fully characterized by IR and NMR spectroscopies and elemental analyses. Their molecular structures were confirmed by single crystal X-ray diffraction analysis. The complexes belong to the relatively unusual zwitterionic, coordination compounds. Moreover, they constitute, as far as we are aware, the first reported examples of palladium compounds bearing N-alkyl-1,3,5-triaza-7-phosphaadamantane ligands. The complexes catalyze efficiently Heck reaction of iodobenzene and n-butyl acrylate as well as iodobenzene and substituted styrenes, under mild conditions in water as a solvent.
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We have investigated the quality of precise orbits for the SARAL altimeter satellite using Satellite Laser Ranging (SLR) and Doppler Orbitography and Radiopositioning Integrated by Satellite (DORIS) data from March 14, 2013 to August 10, 2014. We have identified a 4.31±0.14cm error in the Z (cross-track) direction that defines the center-of-mass of the SARAL satellite in the spacecraft coordinate system, and we have tuned the SLR and DORIS tracking point offsets. After these changes, we reduce the average RMS of the SLR residuals for seven-day arcs from 1.85 to 1.38cm. We tuned the non-conservative force model for SARAL, reducing the amplitude of the daily adjusted empirical accelerations by eight percent. We find that the best dynamic orbits show altimeter crossover residuals of 5.524cm over cycles 7–15. Our analysis offers a unique illustration that high-elevation SLR residuals will not necessarily provide an accurate estimate of radial error at the 1-cm level, and that other supporting orbit tests are necessary for a better estimate. Through the application of improved models for handling time-variable gravity, the use of reduced-dynamic orbits, and through an arc-by-arc estimation of the C22 and S22 coefficients, we find from analysis of independent SLR residuals and other tests that we achieve 1.1–1.2cm radial orbit accuracies for SARAL. The limiting errors stem from the inadequacy of the DPOD2008 and SLRF2008 station complements, and inadequacies in radiation force modeling, especially with respect to spacecraft self-shadowing and modeling of thermal variations due to eclipses.
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