Sensitive CE-MS method for monitoring of riociguat and desmethylriociguat levels in human serum

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.     

Dynamic Interactions in Synthetic Receptors: A Guest Exchange Saturation Transfer Study

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<k_ex<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.     

FEM study of palladium and molybdenum clusters on an alumina covered field emitter

Palladium and molybdenum polycrystalline layers (clusters) have been deposited in a stainless steel UHV system onto a layer of alumina (Al₂O₃). This layer has been prepared by high temperature oxidation of an aluminium layer. The interaction of this system with nitrogen has been investigated at room temperature by an FEM technique. Under these conditions nitrogen spillover from molybdenum to palladium has been observed.     

Infrared picosecond absorption spectroscopy of microcrystalline silicon: separation between carrier recombination in crystalline and amorphous fractions

We have studied ultra-fast carrier dynamics of photo-excited carriers in hydrogenated microcrystalline silicon prepared by a very high frequency glow-discharge technique. We report on direct observation of two types of dynamics using selective photo-excitation in picosecond pump and probe measurements. One type of the observed dynamics has been found to be independent of the sample preparation, while the other reflects the relative weights of crystalline and amorphous fractions. We propose a simple rate-equation model that describes the carrier dynamics in microcrystalline silicon in terms of the composition of those in Si microcrystallites and in the a-Si:H tissue which surrounds the microcrystallites. The model without any fitting parameters reproduces the experimental data very well when the dynamics are scaled with relative volume fractions as obtained from Raman spectra. Received: 23 November 2000 / Accepted: 17 March 2001 / Published online: 23 May 2001     

Diffusion Structural Analysis Study of Titania Films Deposited by Sol-Gel Technique on Silica Glass

The diffusion structural analysis (DSA) was used to characterize microstructure changes of hydrous titania gel films under in situ conditions of heating. TG and DTA were used in order to elucidate the processes controlling the formation of anatase film during heating of hydrous titania gel film. The annealing of porosity and near surface structure defects of the dehydrated titania films was indicated by DSA in the temperature range 255–700°C as the decrease of radon release rate. It was demonstrated that the annealing was enhanced on heating in oxygen in comparison with heating in argon. The DSA experimental results were compared with model curves describing the radon diffusion mobility and the annealing of radon diffusion paths.     

Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization

The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (M_n) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to M_n = 160,000 g mol^?1 for PBA (based on a linear PBA calibration) and up to M_n = 70,000 g mol^?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004     

Generating cryptographically strong Boolean functions using partial information

Periodica Mathematica Hungarica - In our paper we study the usage of partially defined Boolean functions (PDBFs) for generating cryptographically strong Boolean functions. A PDBF can be considered...