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1.
Tomáš Hložek Martin Štícha Miroslava Bursová Ivan Jelínek Petr Tůma Radomír Čabala 《Electrophoresis》2020,41(18-19):1564-1567
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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A series of dinuclear half-sandwich Ru(II), Os(II) and Ir(III) complexes [Ru2(μ-Ln)(η6-pcym)2Cl2](PF6)2 ( 1 , 4 ), [Os2(μ-Ln)(η6-pcym)2Cl2](PF6)2 ( 2 , 5 ) and [Ir2(μ-Ln)(η5-Cp*)2Cl2](PF6)2 ( 3 , 6 ), based on 4,4′-biphenyl-based bridging Schiff base ligands N,N′-(biphenyl-4,4′-diyldimethylidyne)bis-2-(pyridin-2-yl)methanamine (L1; for 1 – 3 ) and N,N′-(biphenyl-4,4′-diyldimethylidyne)bis-2-(pyridin-2-yl)ethanamine (L2; for 4 – 6 ) is reported; pcym = 1-methyl-4-(propan-2-yl)benzene, Cp* = pentamethylcyclopentadienyl. The complexes were characterized by relevant analytical techniques (i.e. elemental analysis, FT-IR, NMR, ESI-MS), and their in vitro cytotoxicity was assessed at six cancerous and two non-cancerous (healthy) human cell lines. Overall, complexes 4 – 6 , containing the L2 bridging ligand, revealed higher cytotoxicity as compared with 1 – 3 and, thus, they were studied in greater detail. The best-performing complex 6 exceeded at least twice the in vitro cytotoxicity of cisplatin and showed high selectivity towards the cancer cells over the normal ones, including the primary culture of human hepatocytes. In contrast to cisplatin, complexes 4 – 6 did not induce the cell cycle modification of the treated A2780 human ovarian carcinoma cells (studied by flow cytometry and Western blot analysis). High levels of superoxide anion were induced by complexes 4 – 6 at the A2780 cells. The levels of activated forms of Caspase-3 and Caspase-8 at the A2780 cells treated by Ru(II) complex 4 were comparable with cisplatin, while complexes 5 and 6 had only a minor effect on activation of these caspases. 相似文献
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Tanja V. Soldatović Enisa Selimović Nevena Milivojević Milena Jovanović Biljana Šmit 《应用有机金属化学》2020,34(10):e5864
The novel heteronuclear complexes [{cis-PtCl (NH3)(μ-pyrazine)ZnCl (terpy)}](ClO4)2 (Pt-L1-Zn) and [{cis-PtCl (NH3)(μ-4,4′-bipyridyl)ZnCl (terpy)}](ClO4)2 (Pt-L2-Zn) (where terpy = 2,2′:6′,2′′-terpyridine, L1 = pyrazine, L2 = 4,4′-bipyridyl) were synthesized and characterized. The pKa values were determined, and based on them it was established that the π-acceptor ability of the pyrazine bridging ligand is more affective on lower pKa values. The kinetic measurements of the substitution reactions with biologically relevant ligands, such as guanosine-5′-monophosphate (5′-GMP), inosine-5′-monophosphate (5′-IMP) and glutathione (GSH), were studied at pH 7.4. The reactions were followed under pseudo-first-order conditions by UV–Vis spectrophotometry. The order of reactivity of the investigated biomolecules for the first reaction is 5′-GMP > 5′-IMP > GSH, while for the second is 5′-IMP > GSH. Pt-L1-Zn complex is more reactive than Pt-L2-Zn. The cytotoxic activity of heteronuclear Pt-L1-Zn and Pt-L2-Zn complexes was determined on human colorectal cancer cell line (HCT-116) and human breast cancer cell line (MDA-MB-231). Both complexes significantly reduced cell viability on tested cell lines and exerted significant cytotoxic effects, with better effect on HCT-116 cells than cisplatin, especially after 72 hr (IC50 < 0.52 μM). The Pt-L2-Zn complex showed higher activity against human breast cancer cells (MDA-MB-231) than cisplatin after 72 hr. The higher reactivity toward DNA constituent and significant cytotoxic activity may be attributed to the different geometry, Lewis acidity of different metal centers, as well as, to choice of bridging ligands. 相似文献
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Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
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We establish a theory of Q -valued functions minimizing a suitable generalization of the Dirichlet integral. In a second paper the theory will be used to approximate efficiently area minimizing currents mod(p) when p = 2Q , and to establish a first general partial regularity theorem for every p in any dimension and codimension . © 2020 Wiley Periodicals LLC. 相似文献
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Dr. Stepas Toliautas Dr. Jelena Dodonova Audrius Žvirblis Ignas Čiplys Artūras Polita Dr. Andrius Devižis Prof. Sigitas Tumkevičius Prof. Juozas Šulskus Dr. Aurimas Vyšniauskas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10342-10349
Molecular rotors are a class of fluorophores that enable convenient imaging of viscosity inside microscopic samples such as lipid vesicles or live cells. Currently, rotor compounds containing a boron-dipyrromethene (BODIPY) group are among the most promising viscosity probes. In this work, it is reported that by adding heavy-electron-withdrawing −NO2 groups, the viscosity-sensitive range of a BODIPY probe is drastically expanded from 5–1500 cP to 0.5–50 000 cP. The improved range makes it, to our knowledge, the first hydrophobic molecular rotor applicable not only at moderate viscosities but also for viscosity measurements in highly viscous samples. Furthermore, the photophysical mechanism of the BODIPY molecular rotors under study has been determined by performing quantum chemical calculations and transient absorption experiments. This mechanism demonstrates how BODIPY molecular rotors work in general, why the −NO2 group causes such an improvement, and why BODIPY molecular rotors suffer from undesirable sensitivity to temperature. Overall, besides reporting a viscosity probe with remarkable properties, the results obtained expand the general understanding of molecular rotors and show a way to use the knowledge of their molecular action mechanism for augmenting their viscosity-sensing properties. 相似文献
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