Lipophilicity measurement of drugs by reversed phase HPLC over Wide pH range using an alkaline-resistant silica-based stationary phase, XBridge Shield RP(18)

We propose a reversed phase HPLC (RP-HPLC) with an alkaline-resistant silica-based stationary phase, XBridge Shield RP(18), for the determination of the lipophilicity of drugs with diverse chemical nature ranging from acidic to basic. A set of 40 model compounds with well-defined solvatochromic parameters was selected to allow a broad distribution of structural properties. The chromatographic results showed that the lipophilicity index log k(w) obtained with XBridge Shield RP(18) was well correlated with experimental log P(oct) values (r(2)=0.96). Linear solvation free-energy relationship (LSER) analyses revealed that the retention mechanism of the stationary phase and 1-octanol/water partitioning were controlled by almost the same balance of intermolecular forces (hydrophobicity as expressed by the van der Waals volume V(w), H-bond acceptor basicity beta, and dipolarity/polarizability pi*). The results showed that XBridge Shield RP(18) phase overcomes the shortcomings of the silica-based stationary phases, the application of which to lipophilicity measurements had been limited to neutral and acidic compounds.     

Extended structure design with simple molybdenum oxide building blocks and urea as a directing agent

We report here a simple one-pot directed synthesis of an oxomolybdate urea composite in which elementary molybdenum oxide building blocks are linked together with the aid of urea. This type of directed material design resulted in large rod-like crystals of an inorganic-organic hybrid extended structure of {MoO 3(NH 2-CO-NH 2)} infinity consisting of right- and left-handed helical units. In the crystal structure urea acts both as a glue that links the inorganic molybdenum units into a helix and as a supramolecular linker for the stabilization of the crystal structure as a whole. This type of molecular topology resulted in an unexpectedly high thermal stability.     

Phase III of solid methane: the orientational potential and rotational tunneling

After many unsuccessful efforts, the structure of solid CD4 III finally has been solved. In this paper, we examine if the known tunneling spectra are consistent with the orientational potentials at the two sites with different symmetries. To this end, we study the rotational kinetic energy of the molecules, construct appropriate pocket states for the tunneling problem, and set up a model potential. Approximate energy levels are obtained from the Ritz variational principle. The agreement between the experimentally determined tunneling frequencies and the calculations is rather good, corroborating the findings of the structural analysis. A continuation of this paper will deal with the partly deuterated methanes.     

Identification of transformation products from β‐blocking agents formed in wetland microcosms using LC‐Q‐ToF

Identification of degradation products from trace organic compounds, which may retain the biological activity of the parent compound, is an important step in understanding the long‐term effects of these compounds on the environment. Constructed wetlands have been successfully utilized to remove contaminants from wastewater effluent, including pharmacologically active compounds. However, relatively little is known about the transformation products formed during wetland treatment. In this study, three different wetland microcosm treatments were used to determine the biotransformation products of the β‐adrenoreceptor antagonists atenolol, metoprolol and propranolol. LC/ESI‐Q‐ToF run in the MS^E and MS/MS modes was used to identify and characterize the degradation products through the accurate masses of precursor and product ions. The results were compared with those of a reference standard when available. Several compounds not previously described as biotransformation products produced in wetlands were identified, including propranolol‐O‐sulfate, 1‐naphthol and the human metabolite N‐deaminated metoprolol. Transformation pathways were significantly affected by microcosm conditions and differed between compounds, despite the compounds' structural similarities. Altogether, a diverse range of transformation products in wetland microcosms were identified and elucidated using high resolving MS. This work shows that transformation products are not always easily predicted, nor formed via the same pathways even for structurally similar compounds. Copyright © 2016 John Wiley & Sons, Ltd.     

Structure-property relationship in stimulus-responsive bolaamphiphile hydrogels

The formation of temperature-, concentration-, and pH-responsive hydrogels composed of the symmetric long-chain bolaamphiphile dotriacontane-1,1'-diyl bis[[2-(dimethylammonio)ethyl]phosphate] (Me(2)PE-C32-Me(2)PE) was investigated by rheological, scattering, and spectroscopic techniques. At pH 5, this bolaamphiphile is known to form a dense network of helically structured nanofibers (K?hler et al. Soft Matter 2006, 2, 77-86). Rheological measurements and dynamic light scattering were used to describe the macroscopic behavior of the hydrogels. Small-angle neutron scattering (SANS) and time-resolved static light scattering were applied to get information about the morphology of the self-assembled aggregates. Finally, solid-state 31P NMR spectroscopy was used to gain insight into the mobility of the bolaamphiphile molecules within the fiber aggregates. In comparison with the previously examined trimethylammonio analogue PC-C32-PC, which forms temperature-dependent hydrogels, Me(2)PE-C32-Me(2)PE exhibits additional concentration- and pH-dependent gelling properties. The significantly higher stability of the Me(2)PE-C32-Me(2)PE hydrogel is supported by the SANS data, which indicate the presence of fiber aggregates up to 50 degrees C.     

General synthesis and aggregation behaviour of a series of single-chain 1,omega-bis(phosphocholines)

The synthesis and physicochemical characterisation of a series of polymethylene-1,omega-bis(phosphocholines) with even-numbered chain lengths between 22 and 32 carbon atoms is described. Two new synthetic strategies for the preparation of long-chain 1,omega-diols as hydrocarbon building blocks are presented. The temperature-dependent self-assembly of the single-chain bolaamphiphiles was investigated by cryo transmission electron microscopy (cryo-TEM), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR).     

Structural studies of TcO2 by neutron powder diffraction and first-principles calculations

Crystalline technetium dioxide was prepared and for the first time its crystal structure determined by neutron powder diffraction. In addition, electronic structure calculations using density functional theory were performed to further elucidate the bonding mechanisms in TcO2. The crystal structure determined by Rietveld analysis with the NPD data is of a distorted rutile type, similar to that of MoO2; space group P21/c, a = 5.6891(1), b = 4.7546(1), c = 5.5195(1) A, and beta = 121.453(1) degrees . The NPD analysis also establishes a new neutron scattering length of 6.00(3) fm for 99Tc. Our results clearly show metal-metal bonding between Tc pairs along the edge-sharing chains of TcO6 octahedra. The Tc-Tc bond was found to be 2.622(1) A from NPD profile analysis and 2.59 A from first-principles DFT calculations. The bond is somewhat longer than expected from earlier predictions, suggesting that the nature of the Tc-Tc interaction is weaker than anticipated for the Tc(IV) cation with three outer electrons. The NPD results supported by the DFT calculations suggest that the filling of antibonding orbitals and the influence of the crystal field stabilization of the d3 Tc cations lead to more regular TcO6 octahedra and diminish the metal-metal bond strength compared with closely related oxides such MoO2 and WO2.     

Revealing the influence of the strength of coulomb interactions on the viscosity and interfacial tension of ionic liquid cosolvent mixtures

Within this work, viscosity and interfacial tension of selected ionic liquid cosolvent mixtures, [EMIM][EtOSO3] (1-ethyl-3-methyl-immidazolium ethyl sulfate) with water and ethanol, were studied as a function of composition by surface light scattering (SLS) and the pendant drop method in a consistent manner, allowing a close insight into the nature of interactions. Here, we show that the viscosity behavior clearly reflects the bulk structure of the ionic liquid cosolvent mixtures and correlates to the fluid structure at the phase boundary. In contrast to former work, we found the viscosity of ionic liquid [EMIM][EtOSO3] to be decreasing the stronger by small amounts of the cosolvents and the lower their dielectric constant. Furthermore, two distinct trends for the dependence of the viscosity on the cosolvent concentration were resolved. These were assigned to ion-dipole interactions dominating in the salt-rich region and to dipole-dipole interactions in the diluted one. A crossover between both regions is reflected by the interfacial tension data, where it seems that up to a "critical" concentration almost no cosolvent is present at the phase boundary.