13C?13C spin–spin coupling constants and 13C isotope effects on 13C chemical shifts in some 4-membered rings

The ¹³C? ¹³C spin–spin coupling constants in natural abundance oxetane, thietane, cyclobutanone, bromo-and chlorocyclobutane have been measured. Furthermore, the ¹³C isotope-induced changes in the chemical shifts of the different ¹³C nuclei in the molecules mentioned above are reported. These shifts are normally to higher magnetic field; in cyclobutanone, however, the resonance of the carbonyl carbon has shifted to lower field because of the substitution of ¹³C?3 for ¹²C?3.     

Influence of mesh deformation on the quality of large eddy simulations

The influence of mesh motion on the quality of large eddy simulation (LES) was studied in the present article. A three‐dimensional, turbulent pipe flow (Re_τ=360) was considered as a test case. Simulations with both stretching and static meshes were carried out in order to understand how mesh motion affects the turbulence statistics. The spatial filtering of static and moving mesh direct numerical simulation (DNS) data showed how an ideal LES would perform, while the comparison of DNS cases with static and moving meshes revealed that no significant numerical errors arise from the mesh motion when the simulation is fully resolved. The comparison of the filtered fields of the DNS with a moving mesh with the corresponding LES fields revealed different responses to mesh motion from different numerical approaches. A straightforward test was applied in order to verify that the moving mesh works consistently in LES: when the mesh is stretched in the streamwise direction, the moving mesh results should be in between the two extremal resolutions between which the mesh is stretched. Numerical investigations using four different LES approaches were carried out. In addition to the Smagorinsky model, three implicit LES approaches were used: linear interpolation (non‐dissipative), the Gamma limiter (dissipative), and the scale‐selective discretisation (slightly dissipative). The results indicate that while the Smagorinsky and the scale‐selective discretisation approaches produce results consistent with the resolution of the non‐static mesh, the implicit LES with linear interpolation or the Gamma scheme do not. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and characterization of amphiphilic triblock copolymers by iron‐mediated atom transfer radical polymerization

The atom transfer radical polymerization of methyl methacrylate (MMA) and n‐butyl methacrylate (n‐BMA) was initiated by a poly(ethylene oxide) chloro telechelic macroinitiator synthesized by esterification of poly(ethylene oxide) (PEO) with 2‐chloro propionyl chloride. The polymerization, carried out in bulk at 90 °C and catalyzed by iron(II) chloride tetrahydrate in the presence of triphenylphosphine ligand (FeCl₂ · 4H₂O/PPh₃), led to A–B–A amphiphilic triblock copolymers with MMA or n‐BMA as the A block and PEO as the B block. A kinetic study showed that the polymerization was first‐order with respect to the monomer concentration. Moreover, the experimental molecular weights of the block copolymers increased linearly with the monomer conversion, and the molecular weight distribution was acceptably narrow at the end of the reaction. These block copolymers turned out to be water‐soluble through the adjustment of the content of PEO blocks (PEO content >90% by mass). When the PEO content was small [monomer/macroinitiator molar ratio (M/I) = 300], the block copolymers were water‐insoluble and showed only one glass‐transition temperature. With an increase in the concentration of PEO (M/I = 100 or 50) in the copolymer, two glass transitions were detected, indicating phase separation. The macroinitiator and the corresponding triblock copolymers were characterized with Fourier transform infrared, proton nuclear magnetic resonance, size exclusion chromatography analysis, dynamic mechanical analysis, and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5049–5061, 2005     

An alternative NMR method to determine nuclear shielding anisotropies for molecules in liquid-crystalline solutions with (13)C shielding anisotropy of methyl iodide as an example

An alternative NMR method for determining nuclear shielding anisotropies in molecules is proposed. The method is quite simple, linear and particularly applicable for heteronuclear spin systems. In the technique, molecules of interest are dissolved in a thermotropic liquid crystal (LC) which is confined in a mesoporous material, such as controlled pore glass (CPG) used in this study. CPG materials consist of roughly spherical particles with a randomly oriented and connected pore network inside. LC Merck Phase 4 was confined in the pores of average diameter from 81 to 375 A and LC Merck ZLI 1115 in the pores of average diameter 81 A. In order to demonstrate the functionality of the method, the (13)C shielding anisotropy of (13)C-enriched methyl iodide, (13)CH(3)I, was determined as a function of temperature using one dimensional (13)C NMR spectroscopy. Methane gas, (13)CH(4), was used as an internal chemical shift reference. It appeared that methyl iodide molecules experience on average an isotropic environment in LCs inside the smallest pores within the whole temperature range studied, ranging from bulk solid to isotropic phase. In contrast, in the spaces in between the particles, whose diameter is approximately 150 microm, LCs behave as in the bulk. Consequently, isotropic values of the shielding tensor can be determined from spectra arising from molecules inside the pores at exactly the same temperature as the anisotropic ones from molecules outside the pores. Thus, for the first time in the solution state, shielding anisotropies can easily be determined as a function of temperature. The effects of pore size as well as of different LC media on the shielding anisotropy are examined and discussed.     

NMR measurements and density functional calculations of the 199Hg-13C spin-spin coupling tensor in methylmercury halides

The isotropic average, JisoHgC, and the anisotropy, DeltaJHgC, of the 199Hg-13C spin-spin coupling tensor in methylmercury halides, CH3HgX (X=Cl, Br, I), were determined for the first time by utilizing the NMR spectra of these molecules dissolved in liquid crystals. Furthermore, density functional calculations were performed using the zeroth-order regular approximation, including also dimethylmercury. The temperature-dependence of the JisoHgC couplings in the isotropic phase was studied in each case in order to extrapolate their values into the liquid crystal state. Good agreement is found between the experimental and the calculated DeltaJHgC values as long as solvent effects are considered in the computations. Most of the magnitude of DeltaJ can be attributed to the spin mechanism of J-coupling, with additional sizable spin-orbital cross terms due to electronic spin-orbit coupling.     

Comparison of virtual high-throughput screening methods for the identification of phosphodiesterase-5 inhibitors

Reliable and effective virtual high-throughput screening (vHTS) methods are desperately needed to minimize the expenses involved in drug discovery projects. Here, we present an improvement to the negative image-based (NIB) screening: the shape, the electrostatics, and the solvation state of the target protein's ligand-binding site are included into the vHTS. Additionally, the initial vHTS results are postprocessed with molecular mechanics/generalized Born surface area (MMGBSA) calculations to estimate the favorability of ligand-protein interactions. The results show that docking produces very good early enrichment for phosphodiesterase-5 (PDE-5); however, in general, the NIB and the ligand-based screening performed better with or without the added electrostatics. Furthermore, the postprocessing of the NIB screening results using MMGBSA calculations improved the early enrichment for the PDE-5 considerably, thus, making hit discovery affordable.     

Critical evaluation of screening techniques for emerging environmental contaminants based on accurate mass measurements with time‐of‐flight mass spectrometry

Emerging contaminants from wastewater effluent samples were analysed, using posttarget and nontarget analysis techniques. The samples were analysed with an ultra performance liquid chromatograph‐time‐of‐flight mass spectrometer (UPLC‐TOF‐MS), and the resulting data were processed with commercial deconvolution software. The method works well for posttarget analysis with prior information about the retention times of the compounds of interest. With positive polarity, 63 of 66 compounds and with negative polarity, 18 of 20 compounds were correctly identified in a spiked sample, while two compounds of a total of 88 fell out of the mass range. Furthermore, a four‐stage process for identification was developed for the posttarget analysis lacking the retention time data. In the process, the number of candidate compounds was reduced by using the accurate mass of selected compounds in two steps (stages 1 and 2), structure–property relationships (stage 3) and isotope patterns of the analytes (stage 4). The process developed was validated by analysing wastewater samples spiked with 88 compounds. This procedure can be used to gain a preliminary indication of the presence of certain analytes in the samples. Nontarget analysis was tested by applying a theoretical mass spectra library for a wastewater sample spiked with six pharmaceuticals. The results showed a high number of false identifications. In addition, manual processing of the data was considered laborious and ineffective. Finally, the posttarget analysis was applied to a real wastewater sample. The analysis revealed the presence of six compounds that were afterwards confirmed with standard compounds as being correct. Three psycholeptics (nordiazepam, oxazepam and temazepam) could be tentatively identified, using the identification process developed. Posttarget analysis with UPLC‐TOF‐MS proved to be a promising method for analysing wastewater samples, while we concluded that the software for nontarget analysis will need improvement before it can be used in environmental analytical work with LC‐TOF‐MS systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural Characteristics of Graphane‐Type C and BN Nanostructures by Periodic Local MP2 Approach

The structural characteristics of fully‐hydrogenated carbon and boron nitride mono‐ and multilayer slabs, together with nanotubes derived from the slabs, are investigated mainly by means of periodic local second‐order Møller–Plesset perturbation (LMP2) calculations and the results are compared with Hartree–Fock (HF), density functional theory (DFT), and dispersion function‐augmented DFT (DFT‐D) obtained ones. The investigated systems are structurally analogous to (111) and (110) slabs of diamond, where the hydrogenated (111) slab of diamond corresponds to the experimentally known graphane. Multilayering of monolayers and nanotubes is energetically favorable at the LMP2 level for both C and BN, while HF and DFT are not able to reproduce this behavior for CH systems. The work highlights the importance of utilizing methods capable of properly describing weak interactions in the investigation of dispersively‐bound systems such as the multilayered graphanes and the corresponding nanotubes.