Polymer bilayer formation due to specific interactions between beta-cyclodextrin and adamantane: a surface force study

The purposes of this study are to utilize the interactions between an adamantane end-capped poly(ethylene oxide) (PEO) and a cationic polymer of beta-cyclodextrin to build polymer bilayers on negatively charged surfaces, and to investigate the interactions between such layers. The association of this system in solution has been studied by rheology, light scattering, and fluorescence measurements. It was found that the adamantane-terminated PEO (PEO-Ad) mixed with the beta-cyclodextrin polymer gives complexes where the interpolymer links are formed by specific inclusion of the adamantane groups in the beta-cyclodextrin cavities. This results in a higher viscosity of the solution and growth of intermolecular clusters. The interactions between surfaces coated with a cationized beta-cyclodextrin polymer across a water solution containing PEO-Ad polymers were studied by employing the interferometric surface force apparatus (SFA). In the first step, the interaction between mica surfaces coated with the cationized beta-cyclodextrin polymer in pure water was investigated. It was found that the beta-cyclodextrin polymer adsorbs onto mica and almost neutralizes the surface charge. The adsorbed layers of the beta-cyclodextrin polymer are rather compact, with a layer thickness of about 60 A (30 A per surface). Upon separation, a very weak attractive force is observed. The beta-cyclodextrin solution was then diluted by pure water by a factor of 3000 and a PEO-Ad polymer was introduced into the solution. Two different architectures of the PEO-Ad polymer were investigated: a four-arm structure and a linear structure. After the adsorption of the PEO polymer onto the beta-cyclodextrin layer reached equilibrium, the forces were measured again. It was found that the weak repulsive long-range force had disappeared and an attractive force caused the surfaces to jump into contact, and that the compressed layer thickness had increased. The attractive force is interpreted as being due to a specific recognition between the hydrophobic adamantane groups on the PEO-Ad polymer and the hydrophobic cavity in the beta-cyclodextrin molecules. Furthermore, the attractive force observed on separation has increased significantly, which is a further indication of a specific interaction between the beta-cyclodextrin polymer and the adamantane groups.     

High-accuracy measurement of specular spectral reflectance and transmittance

The realization of spectrophotometric quantities at the Helsinki University of Technology is based on our reference spectrometer. The reference spectrometer is a high-accuracy instrument developed for measuring spectral specular transmittance and reflectance in a wavelength range extending from ultraviolet to near-infrared. The relative uncertainty estimates for transmittance measurements of neutral-density filters are ca. 0.05%. For spectral reflectance the estimated uncertainties are between 0.14% and 0.34% depending on the sample reflectance and the measurement geometry. We have derived and verified equations that enable both the reflectance and transmittance of various samples to be predicted. Utilizing these equations, the reflectance and transmittance can be accurately calculated for samples with known refractive index. For precise calculations, the characteristics of the measurement beam must be taken into account.     

Interplay of intrinsic, environmental, and dynamic effects in tuning the EPR parameters of nitroxides: further insights from an integrated computational approach

The role of stereoelectronic, environmental, and short-time dynamic effects in tuning the hyperfine and gyromagnetic tensors of a prototypical nitroxide spin probe has been investigated by an integrated computational approach based on extended Lagrangian molecular dynamics and discrete-continuum solvent models. Trajectories were generated in two protic solvents as well as in the gas phase for reference; structural analysis of the dynamics, and comparison with optimized solute-solvent clusters, allowed for the identification of the prevailing solute-solvent hydrogen-bonding patterns and helped to define the strategy for the computation of magnetic parameters. This was performed in a separate step, on a large number of frames, by a high-level DFT approach coupling the PBE0 hybrid functional with a tailored basis set and with proper account of specific and bulk solvent effects. Remarkable changes in solvation networks are found on going from aqueous to methanol solution, thus providing a rationalization of indirect experimentally available evidence. The computed magnetic parameters are in satisfactory agreement with the available measured values and allow for an unbiased evaluation of the role of different effects in tuning the overall EPR observables. Apart from their intrinsic interest, our results pave the route toward the development of tunable detection protocols based on specific spectroscopic signatures.     

Nuclear magnetic shielding and quadrupole coupling tensors in liquid water: a combined molecular dynamics simulation and quantum chemical study

Nuclear magnetic resonance (NMR) shielding tensors for the oxygen and hydrogen nuclei, as well as nuclear quadrupole coupling tensors for the oxygen and deuterium nuclei of water in the liquid and gaseous state, are calculated using Hartree-Fock and density functional theory methods, for snapshots sampled from Car-Parrinello molecular dynamics trajectories. Clusters representing local liquid structures and instantaneous configurations of a single molecule representing low-density gas are fed into a quantum chemical program for the calculation of the NMR tensors. The average isotropic and anisotropic tensorial properties of 400 samples in both states, averaged using a common Eckart coordinate frame, are calculated from the data. We report results for the gas-to-liquid chemical shifts of (17)O and (1)H nuclei, as well as the corresponding change in the nuclear quadrupole couplings of (17)O and (2)H. Full thermally averaged shielding and quadrupole coupling tensors are reported for the gaseous and liquid-state water, for the first time in the case of liquid. Electron correlation effects, the difference of classical vs quantum mechanical rovibrational averaging, and different methods of averaging anisotropic properties are discussed.     

Executive views concerning decision support tools

Support tools for strategic-level decision-making have become increasingly popular. This study investigates the role of OR/MS tools in today’s strategic-level decision support tool market. Executives working in Finland’s 500 largest companies were asked about the decision support tools they use when making major decisions. The responses received indicated that executives actively use a variety of tools, and an average of five different strategic-level tools. Approximately 10% of the tools used could be identified as OR/MS type, these often suit the needs of larger companies with strategic logistical or production functions and compared to other tools, have a specific profile. Executives see advantages in using tools that provide cognitive, collaboration and communication possibilities, and also in using tools that make processes more efficient. OR methodologies have influenced some of the other tools on the market, but ‘soft OR’ tool usage could not be identified. Tools which support creativity are needed.     

Ab initio molecular dynamics study of a mixture of HF(aq) and HCl(aq)

We have studied a mixture of HF and HCl molecules in water using Car-Parrinello ab initio molecular dynamics (CPMD). We have done simulations with 1 HF and 3 HCl molecules, 3 HF and 4 HCl, 6 HF and 8 HCl (6/8 simulation), and 14 HF molecules. All simulations consist of 32 molecules, and they were 10-96 ps long. The HF dissociation probability was around 30%, and HCl's was more than 90%. The solvation of the HF molecule was much better than the solvation of HCl. The solvation environment of F, both the F- ion and the F in HF, did not depend much on the acids concentration, whereas the Cl coordination numbers were rather sensitive to the concentration. In the 6/8 simulation, all XH-Y (X, Y = F, Cl) type molecules were observed and the FH-F was the most probable. In general, the molecular structures in mixed aqueous acid systems were similar to the pure HF(aq) and HCl(aq) systems.