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Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR.  相似文献   
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Lanthanide dinitrogen complexes, Ln(N2) x (x = 1-8), were investigated by Density Functional Theory computations using the B3LYP exchange-correlation functional in conjunction with quasirelativistic pseudopotentials for Ln. After a recent study on the lanthanum complexes (A. Kovács, Structural Chemistry 2018 , 29, 1825), the present study aimed to probe the changes upon variously filled 4f subshells of Ln on the structures, stabilities, and bonding properties in related complexes of Nd, Ho, and Lu. The bonding properties were assessed on the basis of natural atomic charges, Ln valence orbital populations, and analysis of bonding molecular orbitals.  相似文献   
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The European Physical Journal Special Topics - The removal of suspended particles from the interior of a thermocapillary liquid bridge via a finite-particle-size effect restricting the particle...  相似文献   
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We study the full counting statistics of transport electrons through a semiconductor two-level quantum dot with Rashba spin–orbit (SO) coupling, which acts as a nonabelian gauge field and thus induces the electron transition between two levels along with the spin flip. By means of the quantum master equation approach, shot noise and skewness are obtained at finite temperature with two-body Coulomb interaction. We particularly demonstrate the crucial effect of SO coupling on the super-Poissonian fluctuation of transport electrons, in terms of which the SO coupling can be probed by the zero-frequency cumulants. While the charge currents are not sensitive to the SO coupling.  相似文献   
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In this paper, we present an approach of dynamic mesh adaptation for simulating complex 3‐dimensional incompressible moving‐boundary flows by immersed boundary methods. Tetrahedral meshes are adapted by a hierarchical refining/coarsening algorithm. Regular refinement is accomplished by dividing 1 tetrahedron into 8 subcells, and irregular refinement is only for eliminating the hanging points. Merging the 8 subcells obtained by regular refinement, the mesh is coarsened. With hierarchical refining/coarsening, mesh adaptivity can be achieved by adjusting the mesh only 1 time for each adaptation period. The level difference between 2 neighboring cells never exceeds 1, and the geometrical quality of mesh does not degrade as the level of adaptive mesh increases. A predictor‐corrector scheme is introduced to eliminate the phase lag between adapted mesh and unsteady solution. The error caused by each solution transferring from the old mesh to the new adapted one is small because most of the nodes on the 2 meshes are coincident. An immersed boundary method named local domain‐free discretization is employed to solve the flow equations. Several numerical experiments have been conducted for 3‐dimensional incompressible moving‐boundary flows. By using the present approach, the number of mesh nodes is reduced greatly while the accuracy of solution can be preserved.  相似文献   
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The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.  相似文献   
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